EP3327044A1 - Composés azotés quaternisés exempts d'acide et leur utilisation comme additifs pour carburants et lubrifiants - Google Patents
Composés azotés quaternisés exempts d'acide et leur utilisation comme additifs pour carburants et lubrifiants Download PDFInfo
- Publication number
- EP3327044A1 EP3327044A1 EP17198007.1A EP17198007A EP3327044A1 EP 3327044 A1 EP3327044 A1 EP 3327044A1 EP 17198007 A EP17198007 A EP 17198007A EP 3327044 A1 EP3327044 A1 EP 3327044A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- oder
- additive
- hydrocarbyl
- fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000654 additive Substances 0.000 claims abstract description 112
- 239000000446 fuel Substances 0.000 claims abstract description 95
- 230000000996 additive effect Effects 0.000 claims abstract description 73
- 238000002347 injection Methods 0.000 claims abstract description 54
- 239000007924 injection Substances 0.000 claims abstract description 54
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000003599 detergent Substances 0.000 claims abstract description 17
- 239000002816 fuel additive Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000003879 lubricant additive Substances 0.000 claims abstract description 4
- -1 anhydride compound Chemical class 0.000 claims description 315
- 239000002253 acid Substances 0.000 claims description 57
- 239000007795 chemical reaction product Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 239000002283 diesel fuel Substances 0.000 claims description 36
- 229920000768 polyamine Polymers 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 26
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 24
- 238000005956 quaternization reaction Methods 0.000 claims description 21
- 125000001302 tertiary amino group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000008064 anhydrides Chemical class 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 12
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 239000003586 protic polar solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 239000006280 diesel fuel additive Substances 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000004885 piperazines Chemical class 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 description 46
- 238000012360 testing method Methods 0.000 description 44
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- 125000004433 nitrogen atom Chemical group N* 0.000 description 25
- 229920002367 Polyisobutene Polymers 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 23
- 150000001412 amines Chemical class 0.000 description 22
- 150000007513 acids Chemical class 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000002199 base oil Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 150000002924 oxiranes Chemical class 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 125000001931 aliphatic group Chemical group 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 239000010705 motor oil Substances 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 150000001408 amides Chemical class 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 238000005755 formation reaction Methods 0.000 description 12
- 150000003949 imides Chemical class 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 150000003335 secondary amines Chemical class 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 150000004665 fatty acids Chemical group 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 229910052500 inorganic mineral Chemical class 0.000 description 8
- 239000011707 mineral Chemical class 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000003981 vehicle Substances 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical class C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- 150000004985 diamines Chemical group 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000002551 biofuel Substances 0.000 description 5
- 150000001733 carboxylic acid esters Chemical group 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920001083 polybutene Polymers 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003628 tricarboxylic acids Chemical class 0.000 description 5
- 0 *CC(CC(C(*)*IC(N(*)*C[N+](*)(*)*)=O)C([O-])=O)=C* Chemical compound *CC(CC(C(*)*IC(N(*)*C[N+](*)(*)*)=O)C([O-])=O)=C* 0.000 description 4
- 125000004317 1,3,5-triazin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=N1 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 4
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 4
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002368 Glissopal ® Polymers 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
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- 239000003963 antioxidant agent Substances 0.000 description 4
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- 230000001143 conditioned effect Effects 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 4
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
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- 125000004434 sulfur atom Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
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- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 3
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 125000005263 alkylenediamine group Chemical group 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/20—Compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/56—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to novel acid-free quaternized nitrogen compounds, their preparation and use as a fuel and lubricant additive, in particular as a detergent additive, as a wax anti-settling additive (WASA) or as an additive for the reduction of internal diesel injector deposits (IDID); Additive packages containing these compounds; as well as with it additized fuels and lubricants. Furthermore, the present invention relates to the use of these acid-free quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail Injection systems, and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
- a detergent additive as a wax anti-settling additive (WASA) or as an additive for the reduction of internal diesel injector deposits (IDID); Additive packages containing these compounds; as well as with it additized fuels and lubricants.
- IDID internal diesel inject
- direct-injection diesel engines the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber.
- the advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
- the diesel fuel is pumped from a pump with pressures up to 2000 bar into a high-pressure line, the common rail.
- stub lines run to the various injectors that supply the fuel inject directly into the combustion chamber.
- the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible.
- Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value.
- preinjection which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet
- main injection which is responsible in particular for a good torque curve
- post-injection which provides in particular for a low NO x value.
- the fuel is not burned in the rule, but evaporated by residual heat in the cylinder.
- the resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .
- deposits can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the fuel and thereby affect the performance of the engine, ie In particular, reduce the power, but in part also deteriorate the combustion.
- the formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives.
- the WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen atom. or nitrogen atom-containing compound having tertiary amino group, followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid such as in particular acetic acid. Stoichiometric amounts of the acid are required to ensure complete ring opening of the epoxide quaternizing agent and thus quaternization as quantitative as possible.
- a dicarboxylic acid-based acylating agent such as the PIBSA used in the local examples
- an amine such as dimethylaminopropylamine (DMAPA)
- DMAPA dimethylaminopropylamine
- the reaction procedure of the invention allows the complete abandonment of the addition of free acid, in particular free protic acid, which according to the prior art must necessarily be added to the quaternization reagent alkylene oxide.
- the process of the invention namely namely by addition of the nitrogen-containing quaternizable compound to the hydrocarbyl-substituted polycarboxylic anhydride and opening of the anhydride an intramolecularly bound acid function is generated, and it is assumed, without being bound to this model consideration that this intramolecularly generated carboxyl group the alkylene at activates the quaternization reaction and forms by protonation of the resulting after the addition of the alkylene oxide, intermediate alkoxide of the reaction product in the form of a betaine structure.
- the additives according to the invention are superior in many respects to the prior art additives prepared by epoxide / acid quaternization in a conventional manner.
- FIG. 1 shows the performance loss of various diesel fuels in a DW10 engine test. In particular, this is shown for unadditized (squares) or an inventive addit Being compared with a comparison fuel, added with additive according to the prior art at the same dosage (triangles).
- H + donor or “proton donor” refers to any chemical compound that is capable of donating a proton to a proton acceptor. Examples are in particular protic acids, but also water.
- Acid-free for the purposes of the present invention means the absence of low molecular weight inorganic or organic acid and / or its corresponding anion and includes both the lack of acid addition during the production process according to the invention thus also in particular the absence of acid and / or their anion in the quaternized reaction product used as an additive.
- Acid freedom includes, in particular, the absence of stoichiometric amounts of such acids and their anions (stoichiometry based on the quaternizing agent used, in particular the epoxide) and is in particular given when, based on the epoxide quaternizing agent, free acid or its anion is present only in substoichiometric amounts , such as in molar ratios of less than 1: 0.1, or less than 1. 0.01 or 1: 0.001, or 1: 0.0001 of quaternizing agent to acid.
- freedom from acid also includes the complete absence of an inorganic or organic protic acid and / or its anion (i.e., when proton acid and / or its anion is analytically undetectable).
- An "acid" in this context is in particular a free protic acid.
- protic acids examples include inorganic acids or mineral acids such as HCl, H 2 SO 4 , HNO 3 , H 2 CO 3 , and organic carboxylic acids, such as, in particular, monocarboxylic acids of the RCOOH type, where R is a short chain hydrocarbyl radical
- Free or "unbound” acid means that the acid function is not part of a quaternized compound itself, that is, in principle derived from the quaternized compound, e.g. by ion exchange, is separable.
- Typical "anions" of protic acids are, for example, carboxylate anions, such as, for example, acetate and propionate.
- Quadraturear nitrogen groups or amino groups include in particular primary, secondary and tertiary amino groups.
- a “condensation” or “condensation reaction” in the context of the present invention describes the reaction of two molecules with elimination of a smaller molecule, in particular a water molecule. If such cleavage is undetectable, especially in stoichiometric amounts undetectable, and the two molecules nevertheless react, e.g. under addition, the respective reaction of the two molecules takes place "without condensation".
- a “betaine” refers to a particular salt form of a chemical compound that has both a negative and a positive charge in the same molecule, but the charge can not be removed by intramolecular ion transfer.
- IDID stands for "deposits inside injector nozzles" or “internal injector deposits” as seen in modern diesel engines. While conventional (external) deposits are coke-like deposits in the area of the needle tips and injection nozzle holes, deposits are now accumulated inside the injectors and lead to significant performance problems such as blockage of the valve's internal moving parts and associated deterioration or deterioration lack of control of fuel injection, power loss and the like.
- the IDIDs occur both in the form of waxy or soap-like deposits (fatty acid residues and / or C 12 - or C 16 -alkyl succinic acid residues analytically detectable) and in the form of polymer-like carbon deposits. The latter, in particular, have special requirements with regard to their removal / avoidance.
- Cyclic hydrocarbyl radicals may include aromatic or non-aromatic rings and optionally have one or more ring heteroatoms selected from O, S, N, NH.
- “Long chain” or “high molecular weight” hydrocarbyl radicals have a number average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500. They are in particular essentially composed of C 2-6 -, in particular C 2-4 monomer units, such as ethylene, propylene, n- or iso-butylene or mixtures thereof, wherein the various monomers may be randomly distributed or incorporated in polymerized form as blocks.
- Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C 2-6 or poly-C 2-4 -alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are for example also described in the WO2006 / 135881 and the literature quoted there.
- polyalkylene radicals examples include polyisobutenyl radicals derived from so-called "highly reactive" polyisobutenes, which are distinguished by a high content of terminal double bonds. Terminal arranged double bonds are alpha-olefinic double bonds of the type which together are also referred to as vinylidene double bonds.
- Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons.
- Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units.
- such highly reactive polyisobutenes have a number average molecular weight in the range mentioned above.
- the highly reactive polyisobutenes may have a polydispersity in the range of 1.05 to 7, in particular from about 1.1 to 2.5, such as of less than 1.9 or less than 1.5.
- polydispersity is meant the quotient of weight average molecular weight Mw divided by the number average molecular weight Mn.
- Glissopal 2300 2300
- Other number-average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of specific molecular weight ranges.
- Short-chain hydrocarbyl or “low molecular weight hydrocarbyl” in particular represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally one or more times, e.g. 2, 3 or 4 times substituted.
- Short-chain hydrocarbyloxy or “low molecular weight hydrocarbyloxy” in particular represents straight-chain or branched alkyloxy or alkenyloxy, optionally interrupted by one or more, such as e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH- or optionally mono- or polysubstituted, such as. 2, 3 or 4 times substituted.
- Hydrocarbyl or hydroxyhydrocarbyl refers particularly to the hydroxy-substituted analogs of the alkyl or alkenyl radicals defined herein.
- Alkyl or “lower alkyl” in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20 carbon atoms, such as.
- Hydroxyalkyl is in particular the mono- or polysubstituted, especially monohydricated, analogs of the above-mentioned alkyl radicals, such as, for example, the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, e.g. the linear hydroxyalkyl groups having primary hydroxyl group such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.
- Alkenyl is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 20 carbon atoms and a double bond in any position, for.
- C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3 Methyl 3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-1
- Haldroxyalkenyl is in particular the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above alkenyl radicals
- Alkyloxy and alkenyloxy stand especially for the oxygen-linked analogs of the "alkyl” and “alkeny” radicals
- Alkylene represents straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as, for example, C 1 -C 7 -alkylene groups selected from -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 2 -CH (CH 3 ) -, -CH 2 -CH (CH 3 ) -CH 2 -, (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or - CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) - or C 1 -C 4 -alkylene groups selected from -CH 2 -, - (CH 2
- Acyl is radicals derived from straight-chain or branched, optionally mono- or polyunsaturated, optionally substituted C 1 -C 24 -, in particular C 1 -C 12 - or C 1 -C 8 -monocarboxylic acids.
- useful acyl radicals are derived from the following carboxylic acids: saturated acids such as formic, acetic, propionic and n- and i-butyric acid, n- and i-valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, Tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, behenic, lignoceric, cerotic and melissic acids; monounsaturated acids such as acrylic acid, crotonic acid, palmitoleic acid, oleic acid and erucic acid; and diunsaturated acids such as sorbic acid and linoleic acid. If double bonds are present in the fatty acids, these may be in both cis and trans form.
- saturated acids such as formic, acetic, propionic
- Substituents for radicals specified herein are especially selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups.
- Polycarboxylic anhydride compounds in particular polycarboxylic acid anhydrides and hydrocarbyl-substituted polycarboxylic acid anhydrides:
- the anhydride used is derived from any aliphatic di- or polyvalent (such as 3- or 4-valent), in particular of di-, tri- or tetracarboxylic, and optionally by one or more (such as 2 or 3), in particular one long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical substituted.
- Examples are anhydrides of C 3 -C 10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid.
- the anhydrides can also be generated from the corresponding monounsaturated acids and addition of at least one long chain alkyl group and / or high molecular weight hydrocarbyl group.
- suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.
- the hydrophobic "long chain” or “high molecular weight” hydrocarbyl moiety which provides sufficient solubility of the quaternized product in the fuel has a number average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000 such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500.
- Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example having a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.
- Suitable hydrocarbyl-substituted anhydrides are described, for example, in US Pat DE 43 19 672 and the WO2008 / 138836 ,
- Suitable hydrocarbyl-substituted polycarboxylic acid anhydrides also include polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid anhydrides.
- dimeric forms contain two acid anhydride groups which can be reacted independently of one another in the preparation process according to the invention with the quaternizable nitrogen compound.
- Suitable quaternizing agents are, in principle, all compounds suitable as such. In a particular embodiment, however, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides. wherein the R a radicals therein are the same or different and are H or a hydrocarbyl radical, wherein the hydrocarbyl radical has at least 1 to 10 carbon atoms. These are in particular aliphatic or aromatic radicals such as linear or branched C 1- 10 alkyl radicals or aromatic radicals, such as phenyl or C 1-4 alkylphenyl.
- Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-12 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide).
- epoxides as quaternizing these are especially in the absence of free acids, especially in the absence of free protic acids, especially of C 1-12 monocarboxylic acids such as formic acid, acetic acid or propionic acid or C 2-12 dicarboxylic acids such as oxalic acid or adipic acid; or in the absence of sulfonic acids, such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids, such as sulfuric acid or hydrochloric acid.
- the quaternization product thus produced is thus "acid-free" within the meaning of the present invention.
- Suitable "hydroxyalkyl-substituted mono- or polyamines" are those containing at least one, e.g. 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents are equipped.
- hydroxyalkyl-substituted monoamines may be mentioned: N-hydroxyalkyl-monoamines, N, N-dihydroxyalkyl-monoamines and N, N, N-trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above , Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
- hydroxyalkyl-substituted polyamines and especially “hydroxyalkyl-substituted diamines” may be mentioned: (N-hydroxyalkyl) -alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above.
- Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl
- Alkylene stands in particular for ethylene, propylene or butylene.
- Suitable "diamines” are alkylenediamines, as well as the N-alkyl substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N, N or N, N'-dialkylated alkylenediamines.
- Alkylene in particular represents straight-chain or branched C 1-7 or C 1-4 -alkylene, as defined above.
- Alkyl is in particular C 1-4 -alkyl as defined above.
- Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and one or more times, such as a or C 1 -C 4 -alkylated, such as methylated, derivatives of the aforementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA), N, N-diethylaminopropylamine, and N, N-dimethylaminoethylamine.
- DMAPA 3-dimethylamino-1-propylamine
- N-diethylaminopropylamine N, N-dimethylaminoethylamine.
- Suitable straight-chain “polyamines” are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N, N or N, N'-dialkylated Alkylenpolyamine.
- Alkylene in particular represents straight-chain or branched C 1-7 or C 1-4 -alkylene, as defined above.
- Alkyl is in particular C 1-4 -alkyl as defined above.
- Examples are in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenhexamine; and the N, N-dialkyl derivatives thereof, especially the N, N-di-C 1-4 alkyl derivatives thereof.
- N N-dimethyldimethylenetriamine, N, N-diethyldimethylenetriamine, N, N-dipropyldimethylenetriamine, N, N-dimethyldiethylene-1,2-triamine, N, N-diethyldiethylene-1,2-triamine, N, N-dipropyldiethylene-1,2-triamine, N, N-dimethyl-dipropylene-1,3-triamine (ie DMAPAPA), N, N-diethyl-dipropylene-1,3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyldibutylene-1,4-triamine, N, N-diethyldibutylene-1,4-triamine, N, N-dipropyldibutylene-1,4-triamine, N, N-dimethyldipentylene-1,5-triamine, N, N-Diethyl
- Aromatic carbocyclic diamines having two primary amino groups are the di-amino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene, and phenanthrene.
- Aromatic or non-aromatic heterocycles having a primary and a tertiary amino group are, for example, the abovementioned N-heterocycles, which are aminoalkylated on at least one ring N atom, and in particular carry an amino-C 1-4 -alkyl group.
- Aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group are, for example, the abovementioned N-heterocycles, which are hydroxyalkylated on at least one ring N-atom, and in particular a hydroxy-C 1-4 alkyl group.
- Group 1 SURNAME FORMULA Diamines with primary second N atom ethylenediamine 1,2-propylenediamine 1,3-propylene Isomeric butylenediamines, such as 1,5-pentylene Isomeric pentanediamines, such as Isomeric hexanediamines, such as Isomeric heptanediamines, such as Di- and polyamines with secondary second N-atom Diethylenetriamine (DETA) Dipropylenetriamine (DPTA), 3,3'-iminobis (N, N-dimethylpropylamine) Triethylenetetramine (TETA) Tetraethylenepentamine (TEPA) pentaethylenehexamine N-methyl-3-amino-1-propylamine Bishexamethylene triamine in aromatics Diaminobenzenes, such as Diaminopyridines, such as SURNAME FORMULA heterocycles 1- (3-aminopropylenes), such as 1,2-propylenediamine 1,3-propylene
- the reaction of the hydrocarbyl-substituted polycarboxylic anhydride compound with the quaternizable nitrogen compound takes place under thermally controlled conditions, so that essentially no condensation reaction takes place.
- no formation of water of reaction can be observed.
- the reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 ° C.
- the reaction time can be in the range of a few minutes or a few hours, such as about 1 minute to about 10 hours.
- the reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.
- an inert gas atmosphere such as nitrogen, is useful.
- the reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. 0.05 to 0.5 times, e.g. 0.1 to 0.3 fold, molar excess of the anhydride desirable.
- the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are e.g. Solvesso series solvent, toluene or xylene. According to a further particular embodiment, however, the reaction is carried out in the absence of organic solvents, in particular protic solvents.
- the ring opening of the anhydride is carried out with addition of the quaternizable nitrogen compound via its reactive oxygen or nitrogen group (such as hydroxyl group or primary or secondary amine group) and without the elimination of water of condensation.
- the resulting reaction product comprises a polycarboxylic acid intermediate, with at least one newly formed acid amide or ester group and at least one intramolecular, bound, newly formed carboxylic acid or carboxylate group, in stoichiometric proportion to the intramolecularly bound by the addition reaction quaternizable amino group.
- reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.
- reaction step (b) The epoxide-based quaternization according to reaction step (b) is now carried out in complete departure from previously described methods of the prior art without addition of acid.
- the carboxyl radical formed by amine addition supports the epoxide ring opening and thus the quaternization of the amino group.
- the resulting Reaction product thus has no free acid anion. Nevertheless, the product is charge-neutral due to its betaine structure.
- the reaction product or reaction mixture from stage a) is mixed with at least one epoxide compound of the above formula (II), in particular in the required stoichiometric amounts, in order to achieve the desired quaternization.
- Per equivalent of quaternizable tertiary nitrogen atom can be e.g. 0.1 to 1.5 equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent.
- approximately equimolar amounts of the epoxide are used to quaternize a tertiary amine group.
- higher amounts are required to quaternize a secondary or primary amine group.
- reaction time may be in the range of a few minutes or a few hours, e.g. about 10 minutes to about 24 hours.
- the reaction may be carried out at about 0.1 to 20 bar, e.g. 1 to 10 or 1.5 to 3 bar pressure, but especially at about atmospheric pressure.
- an inert gas atmosphere such as e.g. Nitrogen, appropriate.
- the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof for epoxidation, or there may still be a sufficient amount of solvent from reaction step a).
- suitable inert organic aliphatic or aromatic solvent or a mixture thereof for epoxidation or there may still be a sufficient amount of solvent from reaction step a).
- Typical examples are e.g. Solvesso series solvent, toluene or xylene.
- the reaction is carried out in the absence of organic solvents, in particular protic (organic) solvents.
- Protic solvents which in particular are not used according to the invention are, in particular, those having a dielectric constant of greater than 9. Such protic solvents usually contain at least one HO group and can also be hydrous. Typical examples include glycols and glycol ethers and alcohols, such as aliphatic, cyclic-aliphatic, aromatic or heterocyclic alcohols.
- the final reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below), especially since no corrosive, free protic acids are contained in the reaction product.
- the fuel additized with the quaternized additive according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel.
- the fuel may contain other conventional additives to improve the effectiveness and / or wear suppression.
- these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or Solvent.
- the hydrophobic hydrocarbon residue in the above detergent additives which provides the sufficient solubility in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500.
- M n number average molecular weight
- hydrophobic hydrocarbon radical in particular in connection with the polar groups are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n from preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1,500 into consideration.
- monoamino (Da) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in US Pat DE-A 196 20 262 are described.
- Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C 2 - to C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
- Such additives are in particular from the EP-A 307 815 known.
- Such additives are primarily for preventing valve seat wear and can, as in the WO-A 87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.
- Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklakylesters, as described in particular in EP-A 639 632 is described.
- Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
- Polyoxy-C 2 -C 4 -alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 - to C 60 -alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 - alkylamines -C 30, C 1 - to C 30 -Alkylcyclohexanolen or C 1 - to C 30 alkylphenols with from 1 to 30 mol ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
- Such products are used in particular in the EP-A 310 875 .
- polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
- Carboxylic ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular in DE-A 38 38 918 are described.
- mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
- esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol. Such products also meet carrier oil properties.
- the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbon Textreimide with monoamines, Carbonklareimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
- the further detergent additive according to the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure.
- Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
- reaction products with aliphatic polyamines in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
- Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (Di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
- Such "polyisobutene-Mannich bases" are particularly in the EP-A831 141 described.
- One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.
- Co-used carrier oils may be mineral or synthetic.
- Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
- suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
- suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 to C 4 -alkylene groups, which are prepared by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines , by subsequent reductive amination with ammonia, monoamines or polyamines are available.
- EP-A 310 875 Such products are used in particular in the EP-A 310 875 .
- EP-A 356 725 EP-A 700 985 and the US-A 4,877,416 described.
- poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
- carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as are described in particular in US Pat DE-A 38 38 918 are described.
- mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
- esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.
- particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, for.
- suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical.
- Specific examples include tridecanol and nonylphenol.
- Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.
- monohydric aliphatic C 6 -C 18 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers.
- the alcohols can be used both in the form of pure isomers and in the form of technical mixtures.
- a particularly preferred alcohol is tridecanol.
- Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, Butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
- particularly preferred are C 3 to C 4 alkylene oxides, ie, propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
- butylene oxide is used.
- Suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the DE-A 10 102 913 are described.
- Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
- the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
- Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility.
- middle distillates of fossil origin ie for conventional mineral diesel fuels
- used cold flow improvers (“middle distillate flow improvers", "MDFI") come into consideration.
- MDFI middle distillate flow improvers
- WASA wax anti-settling additive
- Suitable C 2 to C 40 olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond.
- the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
- ⁇ -olefins particularly preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
- the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
- olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 to C 40 olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C 10 - to C 40 - ⁇ -olefins are particularly suitable as further olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
- Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
- Suitable carboxylic alkenyl esters are, for example, C 2 -C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters.
- carboxylic acids with a branched hydrocarbon radical are those preferably, whose branching is in the ⁇ -position to the carboxyl group, wherein the ⁇ -carbon atom is particularly preferably tertiary, ie, the carboxylic acid is a so-called neocarboxylic acid.
- the hydrocarbon radical of the carboxylic acid is linear.
- carboxylic alkenyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred.
- a particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").
- copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
- terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as copolymers of class (K1).
- Such terpolymers are in the WO 2005/054314 described.
- a typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
- the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized.
- the majority by weight of the monomer units in the copolymers of class (K1) is thus usually derived from the C 2 to C 40 based olefins.
- the copolymers of class (K1) preferably have a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
- Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms available.
- Other suitable comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
- Suitable comb polymers may also be polyfumarates or polymaleinates.
- homopolymers and copolymers of vinyl ethers are suitable comb polymers.
- suitable comb polymers are, for example, those which are described in the WO 2004/035715 and in " Comb-like polymers. Structure and Properties ", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974 Also mixtures of comb polymers are suitable.
- suitable polyoxyalkylenes are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers, and mixtures thereof.
- these polyoxyalkylene contain at least one, preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000.
- Such polyoxyalkylene compounds are for example in the EP-A 061 895 as well as in the U.S. 4,491,455 described.
- Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000.
- polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable.
- Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR 7 wherein R 7 is C 8 - to C 40 hydrocarbon radical stands.
- the nitrogen substituents can also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
- the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
- suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues
- suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
- amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in US Pat Ullmanns Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
- the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
- the poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups.
- the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
- the carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
- the component of class (K4) is an oil-soluble reaction product based on at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) of the general formula IIa or IIb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 - to C 19 -alkylene group.
- the compounds of the general formula IIa and IIb have in particular the properties of a WASA.
- the preferred oil-soluble reaction product of component (K4) in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
- Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene.
- the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
- C 1 - to C 19 -alkylene groups of the variables B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene ,
- the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
- the primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
- these amines are secondary amines on which the oil-soluble reaction products of component (K4) are based and have the general formula HN (R 8 ) 2 in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals.
- These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
- the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives.
- the two radicals R 8 are the same.
- the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.
- Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine , Dipalmitinamin, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin.
- a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
- component (K4) include the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter may be hydrogenated or unhydrogenated, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or not hydrogenated, called.
- N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter may be hydrogenated or unhydrogenated
- component of class (K4) are cyclic compounds having tertiary amino groups or long-chain primary or condensates secondary amines with carboxylic acid-containing polymers, as described in the WO 93/18115 are described.
- Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of the class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as sulfonate with alkyl-substituted ammonium cations, as described in US Pat EP-A261 957 to be discribed.
- suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized.
- the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
- a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
- Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 described.
- the middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.
- Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in the WO 98/004656 described, and glycerol monooleate. Also in the US Pat. No. 6,743,266 B2 described reaction products of natural or synthetic oils, such as triglycerides, and alkanolamines are suitable as such lubricity improvers.
- Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
- Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
- EO ethylene oxide
- PO propylene oxide
- Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.
- Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
- Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
- Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
- Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
- Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
- Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2 Ethylhexanol, decanol and isotridecanol.
- solvents usually enter the diesel fuel together with the abovementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.
- the additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of internal combustion engines with fuels.
- the quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
- the present invention therefore also fuels, especially middle distillate fuels, with an effective as an additive to achieve beneficial effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially of diesel engines with common rail injection systems, effective content on the quaternized additive according to the invention.
- This effective content (dosage rate) is usually 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel.
- Middle distillate fuels such as diesel fuels or fuel oils
- mineral middle distillate mineral fuels or diesel fuels available through refining
- those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
- the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel).
- biofuel oils biodiesel
- such mixtures are also encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
- Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
- Alkyl esters are usually lower alkyl esters, in particular C 1 - to C 4 alkyl esters, understood by transesterification in plant and / or animal oils and / or fats occurring glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol (“FAME”), are available.
- Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (“RME”).
- PME palm oil methyl ester
- SME soybean oil methyl ester
- RME rapeseed oil methyl ester
- the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.
- gasoline fuels are all commercially available gasoline fuel compositions into consideration.
- a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228.
- petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention.
- the quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.
- the presence of amide or imide in a sample is checked by IR spectrometry.
- the characteristic IR band for amide is 1667 ⁇ 5 cm -1
- the characteristic IR band of the imide is 1705 ⁇ 5 cm -1 .
- the samples were diluted in Solvesso 50% (m / m) and measured in a 29 ⁇ m CaF2 cuvette.
- the power loss was determined according to the official test method CEC F-098-08.
- the power loss is a direct measure of the formation of deposits in the injectors.
- a direct injection diesel engine with common rail system was used according to test methods CEC F-098-08.
- the fuel used was a commercial diesel fuel from Craigrmann (RF-06-03).
- 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors.
- the results illustrate the relative power loss measured at 4000 rpm during a 12-hour continuous operation.
- the value "t0" indicates the power loss normalized (100%) to the value after 10 minutes; the value "t1" indicates the power loss normalized to the value after one hour.
- the storage of diesel fuel in the storage or vehicle tank at temperatures below the cloud point (CP) can precipitate paraffins.
- the resulting paraffin-rich soil phase has a worse cold behavior, can clog filters of vehicles and thus lead to the collapse of the flow rate.
- KS - test a possible sedimentation in vehicle tanks is simulated and visually evaluated. From the paraffin-enriched diesel fuel phase obtained in the test the CP and CFPP value is determined. The comparison of these values with those of the unsedimented fuel allows conclusions to be drawn about the low-temperature behavior of the fuel. Delta CP or Delta CFPP values are determined for this purpose.
- the diesel fuel (DK) to be tested if necessary, is treated for a total of 16 hours at - 13 ° C. There is a visual assessment. Subsequently, 80% by volume of the upper phase of the fuel are carefully removed by suction from above. After heating and homogenizing the remaining 20% subphase, the cloud point (CPKS) and the cold filter plugging point (CFPPKS) are determined therefrom by means of apparatus known per se.
- DK diesel fuel
- CFPPKS cold filter plugging point
- sample vessel scaled measuring cylinder
- sample liquid 550 ml sample liquid.
- the sample is mixed with additive if necessary.
- a water bath is heated to 50 ° C.
- the sample vessel is removed from the water bath and dried. By dropping and shaking the sample is homogenized.
- Subsets are used to determine the initial values CP and CFPP ("Original"). By standing in air, the sample temperature is approximated to 25 ° C.
- the sample vessel with 500 ml sample contents is suspended by means of holding device in a liquid bath. Temperature control starts at 25 ° C.
- the sample is cooled to -13 ° C within 2 h 40 min.
- the sample is stored for 13 h 20 min.
- the sample is aspirated to a residual amount of 100 ml (20%) from above.
- Sample movements and turbulence should be kept as low as possible.
- the sample vessel is heated to 50 ° C with the 20% lower phase remaining therein.
- the lower phase is homogenized and used to determine the final values of CP and CFPP (i.e., CPKS and CFPPKS).
- ESI-LC / MS Electromagnetic Ionization Liquid Chromatography Mass Spectrometry
- the LTQ / FT (Thermo) MS system and LC system consisting of HP 1100 Bin Pump, HP 1100 ALS and HP 1100 DAD are used for this.
- About 10 mg of test substance are dissolved in 1 ml of THF and measured at room temperature. The resolution is 100,000.
- the additive to be tested is mixed with the same amount of the specified motor oil and conditioned at 90 ° C for three days. After this conditioning will be the mixture is filled up with diesel fuel, mixed and assessed by means of the SEDAB test (DGMK Report 531, Annex II-A). The results from both tests allow a statement about the "engine oil compatibility" of the diesel fuel additive to be tested.
- the DK intended for the test and the engine oil shall be assessed before their first use by means of the SEDAB test. To do this, dissolve 10 g motor oil in 500 ml DC. It may be necessary to add 10 ml of alpha-methylnaphthalene to improve the solubility and to repeat the homogenization. This mixture is assessed immediately in the SEDAB test. If the mixture is perfectly filterable, the DK can be used to carry out the test.
- the mixture After conditioning, the mixture is allowed to cool for one hour at room temperature and visually assessed for any precipitation, turbidity, gelation, etc.
- the mixture is made up to 500 ml with diesel fuel and mixed thoroughly. There is a visual assessment. If precipitates have formed, they should be suspended by vigorous shaking before performing the SEDAB test. After two hours, the mixture is again visually assessed and then filtered through a 0.8 micron filter at a pressure difference of 800 mbar (see SEDAB test specification). The total amount must be filterable within the specified time.
- the additive must be classified as non-engine oil compatible. With good filterability and perfect visual findings, the additive is classified as engine oil compatible.
- sample preparation shake the sample vessel of the original fuel sample with 20 vertical strokes. The sample is allowed to stand for 16 hours at room temperature. Immediately before the measurement, the fuel is homogenized again by shaking (10 strokes) and placed in the 500 ml funnel of the test apparatus.
- the membrane filters are conditioned at 90 ⁇ 3 ° C for half an hour in the oven and then stored in a desiccator until needed.
- the appropriately prepared membrane filter is placed in the filtration apparatus.
- the 500 ml funnel is filled with the entire sample (500 ml) and then immediately applied a pressure of 200 hPa (absolute, corresponds to about 800 hPa differential pressure). It is on it to make sure that the fuel sample is not refilled.
- the filtration time is given rounded to full seconds. If a filtration time of two minutes is exceeded without the entire sample being able to be filtered, the test is terminated and the volume of fuel that has passed through until then is measured.
- the result is given as "> 2 minutes” and the sample volume filtered until discontinuation (ml). If the filtration time of the sample is more than two minutes, an appropriate pattern should be heated to 50 ° C for 30 minutes and then filtered. If the measurement result is again over two minutes, the total contamination of the fuel according to DIN 51 419 should be determined.
- funnel and filter are flushed with n-heptane and subsequently with white spirit (40/80) DK-free.
- the membrane filter is carefully removed from the filter plate with tweezers, placed in a clean Petri dish and dried for 30 minutes with half-open lid in a drying oven at 90 ⁇ 3 ° C. Thereafter, the Petri dish is placed in the desiccator for at least 15 minutes to cool.
- Samples which can be filtered within two minutes by the method described above are classified as “non-critical” with respect to the present test method. Diesel fuels that can not be filtered within this time are classified as “critical” and can lead to filter blockages in vehicles and petrol stations.
- the membrane filter should be examined visually (microscopically) or by infrared spectroscopy for the cause of the blockage.
- the additives are used either as a pure substance (as synthesized in the above preparation examples) or in the form of an additive package.
- the following packages were used M2450: Inventive additive package additive Proportion of (%) Product according to Herst. Ex 48.06 dehazers 0.92 antifoam 1.11 Solvesso 150 25.88 Pilot 900 24,03 total 100 additive Proportion of (%) Product according to Herst. Ex. 2 48.06 dehazers 0.92 antifoam 1.11 Solvesso 150 49.91 total 100
- test results are in FIG. 1 shown. Plotted are the t0 values.
- the amide additive according to the invention (diamonds) and the imide comparison additive (triangles) observed that for unadditized fuel (squares)
- the additive of the invention stabilizes the remaining power loss in the range of about 0.5% over the entire duration of the test, ie, 99.5% of the original maximum engine power is maintained.
- the corresponding comparison additive only a power of 98.5% of the original maximum engine power remains.
- the additive to be tested is mixed with the same amount of mineral oil (10 g each), conditioned for 3 days at 90 ° C. and assessed visually. The mixture is then made up to 500 ml with diesel fuel, mixed and evaluated by means of the SEDAB filtration test (likewise defined in DGMK Report 531).
- Test # Product a (from Production Example X) Visually 72h / 90 ° C Solubility in DK filtration 1 2 (comparison) fixed (fail) cloudy, insoluble Fail 2 1 (invention) liquid (pass) soluble passport
- a passenger car with common rail injectors (solenoid type) having injector deposits detected was used to evaluate the additive to remove these internal injector deposits.
- the engine was initially operated on the road with a tank of conventional additABLEm diesel without inventive additive EN590 base fuel (50 liters, 750 km in mixed operation on highways, highways and downtown). There was no improvement in the internal deposits observed when the vehicle was operated on a tank of non-additive fuel (see the table below).
- the tank was operated with the same EN590 base fuel, but with the additive according to the invention was added in a dosage of 120 mg / kg of active material.
- the car was again driven 750 km in mixed operation.
- the deposits were significantly reduced after this test operation with additized fuel after 750 km, as already by a softer, less noisy engine operation was detectable.
- the data read from the engine control unit showed that the amounts of injected fuel decreased to the set point.
- Tank filling + run with non-additive fuel 750 0 rough, loud strong brownish deposits injected fuel volume outside setpoint no improvement, strong deposits (carbonaceous) 1.
- Tank filling + run with additive fuel (dosage 120 mg / kg) 1500 750 less loud reduced deposits injected fuel volume within setpoint reduced deposits 2.
- Tank filling + run with additive fuel (dosage 120 mg / kg) 2250 1500 soft, calm Deposits completely disappeared injected fuel volume within setpoint Deposits completely disappeared
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Abstract
Die vorliegende Erfindung betrifft neuartige säurefreie quaternisierte Stickstoffverbindungen, deren Herstellung und Verwendung als Krafts- und Schmierstoffadditiv, wie insbesondere als Detergensadditiv, als Wachs-Anti-Settling-Additiv (WASA) oder als Additiv zur Verringerung der inneren Dieselinjektorablagerungen (IDID); Additivpakete, welche diese Verbindungen enthalten; sowie damit additivierte Kraft- und Schmierstoffe. Weiterhin betrifft die vorliegende Erfindung die Verwendung dieser säurefreien quaternisierter Stickstoffverbindungen als Kraftstoffzusatz zur Verringerung oder Verhinderung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.The present invention relates to novel acid-free quaternized nitrogen compounds, their preparation and use as a force and lubricant additive, in particular as a detergent additive, as a wax anti-settling additive (WASA) or as an additive for reducing internal diesel injector deposits (IDID); Additive packages containing these compounds; as well as with it additized fuels and lubricants. Furthermore, the present invention relates to the use of these acid-free quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail Injection systems, and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
Description
Die vorliegende Erfindung betrifft neuartige säurefreie quaternisierte Stickstoffverbindungen, deren Herstellung und Verwendung als Kraft- und Schmierstoffadditiv, wie insbesondere als Detergensadditiv, als Wachs-Anti-Settling-Additiv (WASA) oder als Additiv zur Verringerung der internen Dieselinjektorablagerungen (IDID); Additivpakete, welche diese Verbindungen enthalten; sowie damit additivierte Kraft- und Schmierstoffe. Weiterhin betrifft die vorliegende Erfindung die Verwendung dieser säurefreien quaternisierten Stickstoffverbindungen als Kraftstoffzusatz zur Verringerung oder Verhinderung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.The present invention relates to novel acid-free quaternized nitrogen compounds, their preparation and use as a fuel and lubricant additive, in particular as a detergent additive, as a wax anti-settling additive (WASA) or as an additive for the reduction of internal diesel injector deposits (IDID); Additive packages containing these compounds; as well as with it additized fuels and lubricants. Furthermore, the present invention relates to the use of these acid-free quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail Injection systems, and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
Bei direkteinspritzenden Dieselmotoren wird der Kraftstoff durch eine direkt in den Brennraum reichende Mehrloch-Einspritzdüse des Motors eingespritzt und feinst verteilt (vernebelt), anstatt wie beim klassischen (Kammer-)Dieselmotor in eine Vor- oder Wirbelkammer eingeführt zu werden. Der Vorteil der direkteinspritzenden Dieselmotoren liegt in ihrer für Dieselmotoren hohen Leistung und einem dennoch geringen Verbrauch. Außerdem erreichen diese Motoren ein sehr hohes Drehmoment schon bei niedrigen Drehzahlen.In direct-injection diesel engines, the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber. The advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
Zur Zeit werden im Wesentlichen drei Verfahren eingesetzt, um den Kraftstoff direkt in den Brennraum des Dieselmotores einzuspritzen: die konventionelle Verteilereinspritzpumpe, das Pumpe-Düse-System (Unit-Injector-System bzw. Unit-Pump-System) und das Common-Rail-System.Essentially, three methods are currently used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the unit-injector system and the common-rail system. System.
Beim Common-Rail-System wird der Dieselkraftstoff von einer Pumpe mit Drücken bis zu 2000 bar in eine Hochdruckleitung, die Common-Rail gefördert. Ausgehend von der Common-Rail laufen Stichleitungen zu den verschiedenen Injektoren, die den Kraftstoff direkt in den Brennraum injizieren. Dabei liegt auf der Common-Rail stets der volle Druck an, was eine Mehrfacheinspritzung oder eine spezielle Einspritzform ermöglicht. Bei den anderen Injektionssystemen ist dagegen nur eine geringere Variation der Einspritzung möglich. Die Einspritzung beim Common-Rail wird im Wesentlichen in drei Gruppen unterteilt: (1.) Voreinspritzung, durch die im Wesentlichen eine weichere Verbrennung erreicht wird, so dass harte Verbrennungsgeräusche ("Nageln") vermindert werden und der Motorlauf ruhig erscheint; (2.) Haupteinspritzung, die insbesondere für einen guten Drehmomentverlauf verantwortlich ist; und (3.) Nacheinspritzung, die insbesondere für einen geringen NOx-Wert sorgt. Bei dieser Nacheinspritzung wird der Kraftstoff in der Regel nicht verbrannt, sondern durch Restwärme im Zylinder verdampft. Das dabei gebildete Abgas-/Kraftstoffgemisch wird zur Abgasanlage transportiert, wo der Kraftstoff in Gegenwart geeigneter Katalysatoren als Reduktionsmittel für die Stickoxide NOx wirkt.In the common-rail system, the diesel fuel is pumped from a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Starting from the common rail, stub lines run to the various injectors that supply the fuel inject directly into the combustion chamber. In this case, the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible. Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value. In this post injection, the fuel is not burned in the rule, but evaporated by residual heat in the cylinder. The resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .
Durch die variable, zylinderindividuelle Einspritzung kann beim Common-Rail-Einspritzsystem der Schadstoffausstoß des Motors, z.B. der Ausstoß von Stickoxiden (NOx), Kohlenmonoxid (CO) und insbesondere von Partikeln (Ruß), positiv beeinflusst werden. Dies ermöglicht beispielsweise, dass mit Common-Rail-Einspritzsystemen ausgerüstete Motoren der Euro 4-Norm theoretisch auch ohne zusätzlichen Partikelfilter genügen können.Due to the variable, cylinder-specific injection of the common-rail injection system of the pollutant emissions of the engine, such as the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and in particular of particles (soot) are positively influenced. This allows, for example, that equipped with common-rail injection systems engines of Euro 4 standard can theoretically meet without additional particulate filter.
In modernen Common-Rail-Dieselmotoren können sich unter bestimmten Bedingungen, beispielsweise bei Verwendung von biodieselhaltigen Kraftstoffen oder von Kraftstoffen mit Metall-Verunreinigungen wie Zink-Verbindungen, Kupfer-Verbindungen, Bleiverbindungen und weiteren Metallverbindungen , an den Injektoröffnungen Ablagerungen bilden, die das Einspritzverhalten des Kraftstoffs negativ beeinflussen und dadurch die Performance des Motors beeinträchtigen, d.h. insbesondere die Leistung verringern, aber zum Teil auch die Verbrennung verschlechtern. Die Bildung von Ablagerungen wird durch bauliche Weiterentwicklungen der Injektoren, insbesondere durch die Veränderung der Geometrie der Düsen (engere, konische Öffnungen mit abgerundetem Auslass) noch verstärkt. Für eine dauerhaft optimale Funktionsweise von Motor und Injektoren müssen solche Ablagerungen in den Düsenöffnungen durch geeignete Kraftstoffadditive verhindert oder reduziert werden.In modern common-rail diesel engines deposits can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the fuel and thereby affect the performance of the engine, ie In particular, reduce the power, but in part also deteriorate the combustion. The formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives.
Die
Als besonders nachteilig erweist sich bei Befolgung der technischen Lehre der
Andererseits ist aber bekannt, dass Säuren in Kraftstoffadditiven Korrosionsprobleme hervorrufenkönnen (vgl. z.B. Sugiyama et al; SAE International, Technical Paper, Product Code: 2007-01-2027, Date Published: 2007-07-23). Das gemäß
In den Einspritzsystemen modernen Dieselmotoren verursachen Ablagerungen signifikante Performance-Probleme. Weit verbreitet ist die Erkenntnis, dass derartige Ablagerungen in den Sprühkanälen zu einer Verringerung des Kraftstoffflusses und damit zu Leistungsverlusten (power loss) führen können. Ablagerungen an der Injektorspitze beeinträchtigen dagegen die optimale Ausbildung von Kraftstoff-Sprühnebel und bedingen dadurch eine verschlechterte Verbrennung und damit verbunden höhere Emissionen und vermehrten Kraftstoffverbrauch. Im Gegensatz zu diesen herkömmlichen, "äußeren" Ablagerungsphänomenen bereiten auch" interne" Ablagerungen (zusammengefasst als innere Diesel-Injektor-Ablagerungen (IDID)) in bestimmten Teilen der Injektoren, wie an der Düsennadel, am Steuerkolben, am Ventilkolben, am Ventilsitz, an der Ansteuereinheit und an den Führungen dieser Komponenten zunehmend Performance-Probleme. Herkömmliche Additive zeigen eine unzureichende Wirkung gegen diese IDIDs.In the injection systems modern diesel engines cause deposits significant performance problems. It is widely recognized that such deposits in the spray channels can lead to a reduction of the fuel flow and thus to power losses. Deposits on the injector tip, on the other hand, impair the optimum formation of fuel spray and thus cause a deterioration in combustion and, as a result, higher emissions and increased fuel consumption. Unlike these conventional, "Outer" deposition phenomena also present "internal" deposits (collectively referred to as internal diesel injector deposits (IDID)) in certain parts of the injectors, such as the nozzle needle, spool, valve spool, valve seat, drive unit, and guides These components are increasingly having performance issues. Conventional additives show insufficient activity against these IDIDs.
Es besteht daher die Aufgabe, verbesserte quaternisierte Kraftstoffadditive, insbesondere auf der Basis von Hydrocarbyl-substituierten Polycarbonsäureanhydriden, bereitzustellen, welche die genannten Nachteile des Standes der Technik nicht mehr aufweisen.It is therefore an object to provide improved quaternized fuel additives, in particular based on hydrocarbyl-substituted polycarboxylic anhydrides, which no longer have the disadvantages of the prior art mentioned.
Es wurde nun überraschenderweise gefunden, dass obige Aufgabe durch Bereitstellung eines säurefrei durchführbaren Additionsverfahrens zur Herstellung von Epoxidquaternisierten Stickstoff-haltigen Additiven auf der Basis von Hydrocarbyl-substituierten Polycarbonsäureanhydriden und damit reaktiven, quaternisierbare Aminogruppen aufweisenden Verbindungen, und durch die so zugänglichen säurefreien Reaktionsprodukte gelöst werden kann.It has now surprisingly been found that the above object can be achieved by providing an acid-free addition process for the preparation of epoxide-quaternized nitrogen-containing additives based on hydrocarbyl-substituted polycarboxylic anhydrides and thus reactive, quaternizable amino-containing compounds, and by the thus accessible acid-free reaction products ,
Überraschenderweise erlaubt die erfindungsgemäße Reaktionsführung den vollständigen Verzicht auf die Zugabe von freier Säure, insbesondere freier Protonensäure, welche gemäß Stand der Technik zwingend dem Quaternisierungsreagens Alkylenoxid zugesetzt werden muss. Durch die erfindungsgemäße Verfahrensführung wird nämlich durch Addition der stickstoffhaltigen quaternisierbaren Verbindung an das Hydrocarbyl-substituierte Polycarbonsäureanhydrid und Öffnung des Anhydridrings eine intramolekular gebundene Säurefunktion generiert, und man geht davon aus, ohne an diese Modellüberlegung gebunden zu sein, dass diese intramolekular generierte Carboxylgruppe das Alkylenoxid bei der Quaternisierungsreaktion aktiviert und durch Protonierung des nach der Addition des Alkylenoxides entstandenen, intermediären Alkoholates des Reaktionsprodukt in Form einer Betainstruktur bildet.Surprisingly, the reaction procedure of the invention allows the complete abandonment of the addition of free acid, in particular free protic acid, which according to the prior art must necessarily be added to the quaternization reagent alkylene oxide. By the process of the invention namely namely by addition of the nitrogen-containing quaternizable compound to the hydrocarbyl-substituted polycarboxylic anhydride and opening of the anhydride an intramolecularly bound acid function is generated, and it is assumed, without being bound to this model consideration that this intramolecularly generated carboxyl group the alkylene at activates the quaternization reaction and forms by protonation of the resulting after the addition of the alkylene oxide, intermediate alkoxide of the reaction product in the form of a betaine structure.
Überraschenderweise sind die so hergestellten erfindungsgemäßen Additive den in konventioneller Weise durch Epoxid/Säure-Quaternisierung hergestellten Additive gemäß Stand der Technik in mehrfacher Hinsicht überlegen.Surprisingly, the additives according to the invention thus prepared are superior in many respects to the prior art additives prepared by epoxide / acid quaternization in a conventional manner.
Die vorliegende Erfindung betrifft insbesondere folgende spezielle Ausführungsformen:
- 1. Verfahren zur Herstellung quaternisierter Stickstoffverbindungen, wobei man
- a. an eine Polycarbonsäureanhydrid-Verbindung, insbesondere ein Polycarbonsäureanhydrid oder ein Hydrocarbyl-substituiertes Polycarbonsäureanhydrid, wie insbesondere ein Polyalkylen-substituiertes Polycarbonsäureanhydrid, eine Verbindung, enthaltend wenigstens eine, mit dem Anhydrid reaktive Sauerstoff- oder Stickstoff-haltige Gruppe, wie z.B. eine -OH und/oder eine primäre oder sekundäre Aminogruppe, und zusätzlich enthaltend wenigstens eine quaternisierbare Aminogruppe, addiert und
- b. das Produkt aus Stufe a) mit einem insbesondere H+-Donor-freien und vor allem säurefreien Quaternisierungsmittel quaternisiert.
- 2. Verfahren nach Ausführungsform 1, wobei die Polycarbonsäureanhydrid-Verbindung ein Di-, Tri- oder Tetracarbonsäure-Anhydrid ist.
- 3. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei die Polycarbonsäureanhydrid-Verbindung das Anhydrid einer C4-C10-Dicarbonsäure ist.
- 4. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei die Polycarbonsäureanhydrid-Verbindung wenigstens einen hochmolekularen Hydrocarbyl-, insbesondere Polyalkylen-Substituenten mit einem zahlenmittleren Molekulargewicht (Mn) im Bereich von etwa 200 bis 10.000, wie z.B. 300 bis 8.000, insbesondere 350 bis 5.000, umfasst.
- 5. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei die mit dem Anhydrid reaktive Verbindung ausgewählt ist unter
- a. mit niedermolekularem Hydroxyhydrocarbyl, insbesondere niedermolekularem Hydroxyalkyl substituierten Mono- oder Polyaminen mit wenigstens einer quaternisierbaren, primären, sekundären oder tertiären Aminogruppe
- b. geradkettigen oder verzweigtem, cyclischen, heterocyclischen, aromatischen oder nichtaromatischen Polyaminen mit wenigstens einer primären oder sekundären (anhydridreaktiven) Aminogruppe und mit wenigstens einer quaternisierbaren, primären, sekundären oder tertiären Aminogruppe;
- c. Piperazinen.
- 6. Verfahren nach Ausführungsform 5, wobei die mit dem Anhydrid reaktive Verbindung ausgewählt ist unter
- a. mit niedermolekularem Hydroxyhydrocarbyl, insbesondere niedermolekularem Hydroxyalkyl substituierten primären, sekundären oder tertiären Monoaminen und Hydroxyalkyl-substituierten primären, sekundären oder tertiären Diaminen.
- b. geradkettigen oder verzweigten aliphatischen Diaminen mit zwei primären Aminogruppen; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer sekundären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer tertiären Aminogruppe; aromatischen carbocyclischen Diaminen mit zwei primären Aminogruppen; aromatischen heterocyclischen Polyaminen mit zwei primären Aminogruppen; aromatischen oder nichtaromatischen Heterozyklen mit einer primären und einer tertiären Aminogruppe.
- 7. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei das Quaternisierungsmittel ausgewählt ist unter Epoxiden, insbesondere Hydrocarbyl-substituierten Epoxiden.
- 8. Verfahren nach Ausführungsform 7, wobei die Quaternisierung ohne Zugabe eines H+-Donors, insbesondere ohne Zugabe von Säure erfolgt.
- 9. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei man Stufe a), d.h. die Additionsreaktion, bei einer Temperatur von weniger als etwa 80 °C und insbesondere bei einer Temperatur im Bereich von etwa 30 bis 70 °C, vor allem 40 bis 60 °C, durchführt.
- 10. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei man Stufe a) über einem Zeitraum von 1
Minute bis 10 Stunden oder 10 Minuten bis 5 Stunden oder 10Minuten bis 4Stunden oder 2 bis 3 Stunden durchführt. - 11. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei man Stufe b), d.h. die die Quaternisierung, bei einer Temperatur im Bereich von 40 bis 80 °C durchführt.
- 12. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei man Stufe b) über einen Zeitraum 1
bis 10 Stunden durchführt. - 13. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei man Stufe b) mit einem Epoxid, insbesondere niedermolekularen Hydrocarbylepoxid, als Quaternisierungsmittel in Abwesenheit von (stöchiometrischen Mengen) freier (von der Polycarbonsäureverbindung verschiedener) Säure durchführt.
- 14. Verfahren nach einer der vorhergehenden Ausführungsformen, wobei die Umsetzung gemäß Stufe a) und/oder b) in Abwesenheit eines Lösungsmittels, insbesondere in Abwesenheit eines organischen protischen Lösungsmittels erfolgt.
- 15. Quaternisierte Stickstoffverbindung oder Reaktionsprodukt, erhältlich nach einem Verfahren nach einer der vorhergehenden Ausführungsformen.
- 16. Quaternisierte Stickstoffverbindung oder Reaktionsprodukt nach Ausführungsform 15, umfassend wenigstens eine Verbindung der allgemeinen Formeln:
oder
worin- R1 für H oder geradkettigen oder verzweigten Hydrocarbyl-Rest steht, welcher gegebenenfalls ein- oder mehrfach substituiert sein kann mit Hydroxyl, Carboxyl, Hydrocarbyloxy-und/oder Acyl-Resten, oder ein oder mehrere Ethergruppen in der Hydrocarbylkette aufweist, und insbesondere für H oder kurzkettiges Hydrocarbyl, insbesondere Alkyl steht;
- R2 für H oder Alkyl steht; R3 für Hydrocarbyl, insbesondere langkettiges Hydrocarbyl, wie z.B. für einen Polyalkylenrest steht;
- wenigstens einer der Reste R4, R5 und R6 ein durch Quaternisierung eingeführter Rest ist, insbesondere eine niedermolekularen Hydrocarbylrest oder niedermolekularen Hydroxyl-substituierter Hydrocarbylrest ist, und die übrigen Reste ausgewählt sind unter geradkettigen oder verzweigten niedermolekularen Hydrocarbylresten, zyklischen Hydrocarbylresten, welche gegebenenfalls eine oder mehrfach substituiert sind und/oder ein oder mehrere Heteroatome aufweisen;
- R7 für H oder einen geradkettigen oder verzweigten niedermolekularen Hydrocarbyl-Rest steht, welcher gegebenenfalls ein oder mehrfach, wie z.B. 2-, 3- oder 4-fach, substituiert sein kann mit gleichen oder verschiedenen Hydroxyl-, Carboxyl-, niedermolekularen Hydrocarbyloxy- und/oder Acyl-Resten, oder ein oder mehrere Ethergruppen in der Hydrocarbylkette aufweist, oder R7 zusammen mit einem der Reste R4, R5 und R6 eine Brückengruppe, z.B. eine Alkylen- oder Alkenylen-Gruppe bildet;
- L1 für eine chemische Bindung oder geradkettige oder verzweigte Alkylengruppe steht und
- L2 für eine geradkettige oder verzweigte Alkylengruppe steht, die gegebenenfalls ein oder mehrere Heteroatome, insbesondere ausgewählt unter - O- und -NH- oder Substituenten trägt.
- 17. Quaternisierte Stickstoffverbindung oder Reaktionsprodukt nach Ausführungsform 15 oder 16, welche(s) im Wesentlichen H+-Donor-frei, insbesondere im Wesentlichen säurefrei ist, und insbesondere keine anorganischen Säuren oder kurzkettigen organischen Säuren aufweist.
- 18. Verwendung einer quaternisierten Stickstoffverbindung oder eines Reaktionsproduktes nach einer der Ausführungsformen 15 bis 17 als Kraftstoffadditiv oder Schmierstoffadditiv.
- 19. Verwendung nach Ausführungsform 18, als Detergensadditiv für Dieselkraftstoffe.
- 20. Verwendung nach Ausführungsform 18, als Wachs-Anti-Settling Additiv (WASA) für Mitteldestillatbrennstoffe, insbesondere Dieselkraftstoffe.
- 21. Verwendung nach Ausführungsform 19, als Additiv zur Verringerung oder Vermeidung von Ablagerungen in Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.
- 22. Verwendung nach Ausführungsform 21, als Additiv zur Kontrolle (Vermeidung oder Verringerung, insbesondere teilweise, im wesentlichen vollständige oder vollständige Verringerung) vom internen Diesel-Injektor-Ablagerungen (IDID), dh. Ablagerungen im Inneren des Injektors; insbesondere von wachs- oder seifenarigen Ablagerungen und/oder kohlenstoffartigen polymeren Ablagerungen.
- 23. Additivkonzentrat, enthaltend in Kombination mit weiteren Kraftstoffadditiven, insbesondere Dieselkraftstoffadditiven, wenigstens eine quaternisierte Stickstoffverbindung oder ein Reaktionsprodukt nach einer der Ausführungsformen 15 und 16.
- 24. Kraftstoffzusammensetzung, enthaltend in einer Hauptmenge eines übliches Grundkraftstoffs eine (detergens-) wirksame Menge wenigstens einer quaternisierten Stickstoffverbindung oder eines Reaktionsproduktes nach einer der Ausführungsformen 15 und 16.
- 25. Schmierstoffzusammensetzung, enthaltend in einer Hauptmenge eines übliches Schmierstoffs eine (detergens-) wirksame Menge wenigstens einer quaternisierten Stickstoffverbindung oder eines Reaktionsproduktes nach einer der Ausführungsformen 15 und 16.
- 1. A process for preparing quaternized nitrogen compounds, wherein
- a. a polycarboxylic anhydride compound, in particular a polycarboxylic anhydride or a hydrocarbyl-substituted polycarboxylic anhydride, in particular a polyalkylene-substituted polycarboxylic anhydride, a compound containing at least one anhydride-reactive oxygen or nitrogen-containing group, such as a -OH and / or a primary or secondary amino group, and additionally containing at least one quaternizable amino group, added and
- b. the product from stage a) is quaternized with a quaternizing agent which is in particular H + -donor-free and, above all, acid-free.
- 2. The method of embodiment 1, wherein the polycarboxylic acid anhydride compound is a di-, tri- or tetracarboxylic anhydride.
- 3. The method according to any one of the preceding embodiments, wherein the polycarboxylic anhydride compound is the anhydride of a C 4 -C 10 dicarboxylic acid.
- 4. A process according to any one of the preceding embodiments, wherein the polycarboxylic anhydride compound comprises at least one high molecular weight hydrocarbyl, especially polyalkylene, substituent of number average molecular weight (Mn) in the range of about 200 to 10,000, such as 300 to 8,000, especially 350 to 5,000, includes.
- 5. The method according to any one of the preceding embodiments, wherein the reactive with the anhydride compound is selected from
- a. with low molecular weight hydroxyhydrocarbyl, in particular low molecular weight hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group
- b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternizable, primary, secondary or tertiary amino group;
- c. Piperazines.
- 6. The method of embodiment 5, wherein the reactive with the anhydride compound is selected from
- a. with low molecular weight hydroxyhydrocarbyl, in particular low molecular weight hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines.
- b. straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group.
- 7. The method according to any one of the preceding embodiments, wherein the quaternizing agent is selected from epoxides, in particular hydrocarbyl-substituted epoxides.
- 8. Process according to embodiment 7, wherein the quaternization takes place without addition of an H + donor, in particular without addition of acid.
- 9. A process according to any one of the preceding embodiments, wherein step a), ie the addition reaction, at a temperature of less than about 80 ° C and in particular at a temperature in the range of about 30 to 70 ° C, especially 40 to 60 ° C, performs.
- 10. The method according to any one of the preceding embodiments, wherein one carries out stage a) over a period of 1 minute to 10 hours or 10 minutes to 5 hours or 10 minutes to 4 hours or 2 to 3 hours.
- 11. The method according to any one of the preceding embodiments, wherein one carries out stage b), that is, the quaternization, at a temperature in the range of 40 to 80 ° C.
- 12. The method according to any one of the preceding embodiments, wherein one carries out stage b) over a period of 1 to 10 hours.
- 13. The method according to any one of the preceding embodiments, wherein one carries out stage b) with an epoxide, in particular low molecular weight hydrocarbyl epoxide, as a quaternizing agent in the absence of (stoichiometric amounts) of free (different from the polycarboxylic acid) acid.
- 14. The method according to any one of the preceding embodiments, wherein the reaction according to step a) and / or b) takes place in the absence of a solvent, in particular in the absence of an organic protic solvent.
- 15. A quaternized nitrogen compound or reaction product obtainable by a process according to any one of the preceding embodiments.
- 16. Quaternized nitrogen compound or reaction product according to embodiment 15, comprising at least one compound of the general formulas:
or
wherein- R 1 is H or straight-chain or branched hydrocarbyl radical which may optionally be monosubstituted or polysubstituted by hydroxyl, carboxyl, hydrocarbyloxy and / or acyl radicals, or has one or more ether groups in the hydrocarbyl chain, and in particular H or short-chain hydrocarbyl, in particular alkyl;
- R 2 is H or alkyl; R 3 is hydrocarbyl, in particular long-chain hydrocarbyl, such as a polyalkylene radical;
- at least one of R 4 , R 5 and R 6 is a radical introduced by quaternization, in particular a low molecular weight hydrocarbyl radical or low molecular weight hydroxyl-substituted hydrocarbyl radical, and the remaining radicals are selected from straight-chain or branched low-molecular weight hydrocarbyl radicals, cyclic hydrocarbyl radicals which may optionally be one or polysubstituted and / or having one or more heteroatoms;
- R 7 is H or a straight-chain or branched low molecular weight hydrocarbyl radical which may be optionally substituted one or more times, such as 2-, 3- or 4-fold, with identical or different hydroxyl, carboxyl, low molecular weight hydrocarbyloxy and or acyl radicals, or one or more ether groups in the hydrocarbyl chain, or R 7 together with one of the radicals R 4 , R 5 and R 6 forms a bridging group, for example an alkylene or alkenylene group;
- L 1 represents a chemical bond or straight or branched alkylene group and
- L 2 is a straight-chain or branched alkylene group which optionally bears one or more heteroatoms, in particular selected from -O- and -NH- or substituents.
- 17. Quaternized nitrogen compound or reaction product according to embodiment 15 or 16, which is (s) substantially H + donor-free, in particular substantially free of acid, and in particular no inorganic acids or short-chain organic acids.
- 18. Use of a quaternized nitrogen compound or a reaction product according to any one of embodiments 15 to 17 as a fuel additive or lubricant additive.
- 19. Use according to embodiment 18, as a detergent additive for diesel fuels.
- 20. Use according to embodiment 18, as a wax anti-settling additive (WASA) for middle distillate fuels, in particular diesel fuels.
- 21. Use according to embodiment 19, as an additive for reducing or avoiding deposits in injection systems of direct-injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines with common-rail injection systems, and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
- 22. Use according to embodiment 21, as an additive for control (avoidance or reduction, in particular partial, substantially complete or complete reduction) of internal diesel injector deposits (IDID), ie. Deposits inside the injector; in particular of waxy or soap-like deposits and / or carbonaceous polymeric deposits.
- 23. Additive concentrate, comprising in combination with further fuel additives, in particular diesel fuel additives, at least one quaternized nitrogen compound or a reaction product according to any one of embodiments 15 and 16.
- A fuel composition comprising, in a major amount of a common base fuel, a (detergent) effective amount of at least one quaternized nitrogen compound or reaction product according to any of embodiments 15 and 16.
- 25. A lubricant composition comprising, in a major amount of a common lubricant, a (detergent) effective amount of at least one quaternized nitrogen compound or a reaction product according to any of embodiments 15 and 16.
Ein"H+-Donor" oder "Protonendonor" bezeichnet jegliche chemische Verbindung, welche in der Lage ist, ein Proton an einen Protonen-Akzeptor abzugeben. Beispiele sind insbesondere Protonensäuren, aber auch Wasser.An "H + donor" or "proton donor" refers to any chemical compound that is capable of donating a proton to a proton acceptor. Examples are in particular protic acids, but also water.
"Säurefrei" bedeutet im Sinne der vorliegenden Erfindung das Fehlen von niedermolekularer anorganischer oder organischer Säure und/oder von deren korrespondierendem Anion und umfasst sowohl die fehlende Zugabe von Säure während des erfindungsgemäßen Herstellungsverfahrens also auch insbesondere das Fehlen von Säure und/oder von deren Anion in dem als Additiv verwendeten quaternisierten Reaktionsprodukt. Säurefreiheit umfasst insbesondere das Fehlen von stöchiometrischen Mengen solcher Säuren und deren Anionen (Stöchiometrie bezogen auf das eingesetzte Quaternisierungsmittel, wie insbesondere das Epoxid) und ist insbesondere gegeben, wenn, bezogen auf eingesetztes Epoxid-Quaternsierungsmittel, freie Säure oder deren Anion nur in substöchiometrischen Mengen vorliegt, wie z.B. in molaren Verhältnissen von weniger als 1 : 0,1, oder weniger als 1. 0,01 oder 1:0,001, oder 1:0,0001 von Quaternisierungsmittel zu Säure. Säurefreiheit umfasst insbesondere auch das vollständige Fehlen einer anorganischen oder organischen Protonensäure und/oder deren Anions (d.h. wenn Protonensäure und/oder deren Anion analytisch nicht mehr nachweisbar ist). Eine "Säure" in diesem Zusammenhang ist insbesondere eine freie Protonensäure."Acid-free" for the purposes of the present invention means the absence of low molecular weight inorganic or organic acid and / or its corresponding anion and includes both the lack of acid addition during the production process according to the invention thus also in particular the absence of acid and / or their anion in the quaternized reaction product used as an additive. Acid freedom includes, in particular, the absence of stoichiometric amounts of such acids and their anions (stoichiometry based on the quaternizing agent used, in particular the epoxide) and is in particular given when, based on the epoxide quaternizing agent, free acid or its anion is present only in substoichiometric amounts , such as in molar ratios of less than 1: 0.1, or less than 1. 0.01 or 1: 0.001, or 1: 0.0001 of quaternizing agent to acid. In particular, freedom from acid also includes the complete absence of an inorganic or organic protic acid and / or its anion (i.e., when proton acid and / or its anion is analytically undetectable). An "acid" in this context is in particular a free protic acid.
Beispiele typischer "Protonensäuren" umfassen anorganische Säuren oder Mineralsäuren, wie HCl, H2SO4, HNO3, H2CO3, und organische Carbonsäuren, wie insbesondere Monocarbonsäuren des Typs RCOOH, worin R für einen kurzkettigen Hydrocarbylrest stehtExamples of typical "protic acids" include inorganic acids or mineral acids such as HCl, H 2 SO 4 , HNO 3 , H 2 CO 3 , and organic carboxylic acids, such as, in particular, monocarboxylic acids of the RCOOH type, where R is a short chain hydrocarbyl radical
"Freie" oder "ungebundene" Säure bedeutet, dass die Säurefunktion nicht Bestandteil einer quaternisierten Verbindung selbst ist, also grundsätzlich von der Quaternisierten Verbindung, z.B. durch lonenaustausch, abtrennbar ist."Free" or "unbound" acid means that the acid function is not part of a quaternized compound itself, that is, in principle derived from the quaternized compound, e.g. by ion exchange, is separable.
Typischen "Anionen" von Protonensäuren sind z.B. Carboxylatanionen, wie z.B. Acetat und Propionat.Typical "anions" of protic acids are, for example, carboxylate anions, such as, for example, acetate and propionate.
"Quaternisierbare" Stickstoffgruppen oder Aminogruppen umfassen insbesondere primäre, sekundäre und tertiäre Aminogruppen."Quaternizable" nitrogen groups or amino groups include in particular primary, secondary and tertiary amino groups.
Eine "Kondensation" oder "Kondensationsreaktion" im Sinne der vorliegenden Erfindung beschreibt die Umsetzung von zwei Molekülen unter Abspaltung eines kleineren Moleküls, insbesondere eines Wasser-Moleküls. Ist eine derartige Abspaltungnicht nachweisbar, insbesondere in stöchiometrischen Mengen nicht nachweisbar, und die beiden Moleküle reagieren trotzdem, z.B. unter Addition, so erfolgt die betreffende Umsetzung der beiden Moleküle "ohne Kondensation" .A "condensation" or "condensation reaction" in the context of the present invention describes the reaction of two molecules with elimination of a smaller molecule, in particular a water molecule. If such cleavage is undetectable, especially in stoichiometric amounts undetectable, and the two molecules nevertheless react, e.g. under addition, the respective reaction of the two molecules takes place "without condensation".
Ein "Betain" bezeichnet eine spezielle Salzform einer chemischen Verbindung, die sowohl eine negative als auch eine positive Ladung in ein und demselben Molekül aufweist, wobei die Ladung durch intramolekularen lonentransfer jedoch nicht aufgehoben werden kann.A "betaine" refers to a particular salt form of a chemical compound that has both a negative and a positive charge in the same molecule, but the charge can not be removed by intramolecular ion transfer.
"IDID" steht für "Ablagerungen in Inneren von Einspritzdüsen" oder "internen Einspritzdüsenablagerungen" wie sie bei modernen Dieselmotoren zu beobachten sind. Während herkömmliche (äußere) Ablagerungen koksartige Ablagerungen im Bereich der Nadelspitzen und der Sprühlöcher der Einspritzdüsen darstellen, treten zwischenzeitlich gehäuft Ablagerungen im Inneren der Einspritzdüsen auf und führen zu signifikanten Performance-Problemen, wie z.B. Blockierung der inneren beweglichen Teile des Ventils und damit verbunden verschlechterte oder fehlende Kontrolle der Kraftstoffinjektion, Kraftverlust und dergleichen. Die IDIDs treten sowohl in Form wachs- oder seifenartiger Ablagerungen (Fettsäurereste und/oder C12- oder C16-Alkyl-Bernsteinsäurereste analytisch nachweisbar) als auch in Form polymerartiger Kohlenstoff-Ablagerungen auf. Insbesondere letztere stellen besondere Anforderungen hinsichtlich ihrer Entfernung/Vermeidung."IDID" stands for "deposits inside injector nozzles" or "internal injector deposits" as seen in modern diesel engines. While conventional (external) deposits are coke-like deposits in the area of the needle tips and injection nozzle holes, deposits are now accumulated inside the injectors and lead to significant performance problems such as blockage of the valve's internal moving parts and associated deterioration or deterioration lack of control of fuel injection, power loss and the like. The IDIDs occur both in the form of waxy or soap-like deposits (fatty acid residues and / or C 12 - or C 16 -alkyl succinic acid residues analytically detectable) and in the form of polymer-like carbon deposits. The latter, in particular, have special requirements with regard to their removal / avoidance.
Werden keine gegenteiligen Angaben gemacht, so gelten folgende allgemeine Bedeutungen:
- "Hydrocarbyl" ist breit auszulegen und umfasst sowohl langkettige als auch kurzkettige, gerade oder verzweigte Kohlenwasserstoffreste, welche ggf. zusätzlich Heteroatome, wie z.B. O, N, NH,S, in ihrer Kette enthalten können.
- "Hydrocarbyl" is to be interpreted broadly and includes both long-chain and short-chain, straight or branched hydrocarbon radicals, which may optionally contain additional heteroatoms, such as O, N, NH, S, in their chain.
"Zyklische Hydrocarbylreste" können aromatische oder nichtaromatischen Ringe umfassen und gegebenenfalls ein oder mehrere Ringheteroatome, ausgewählt unter O, S, N, NH aufweisen."Cyclic hydrocarbyl radicals" may include aromatic or non-aromatic rings and optionally have one or more ring heteroatoms selected from O, S, N, NH.
"Langkettige" oder "hochmolekulare" Hydrocarbylreste haben ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, wie z.B. 113 bis 10.000, oder 200 bis 10.000 oder 350 bis 5.000, wie z.B. 350 bis 3.000, 500 bis 2.500, 700 bis 2.500, oder 800 bis 1.500. Sie sind insbesondere im Wesentlichen aus C2-6-, insbesondere C2-4-Monomerbausteinen, wie Ethylen, Propylen, n- oder iso-Butylen oder Mischungen davon aufgebaut, wobei die verschiedenen Monomere statistisch verteilt oder als Blöcke einpolymerisiert enthalten sein können. Derartige langkettige Hydrocarbylreste werden auch als Polyalkylenreste oder Poly-C2-6- oder Poly-C2-4-alkylenreste bezeichnet. Geeignete langkettige Hydrocarbylreste und deren Herstellung sind beispielsweise auch beschreiben in der
Beispiele für besonders brauchbare Polyalkylen-Reste sind Polyisobutenyl-Reste, abgeleitet von sogenannten "hochreaktiven" Polyisobutenen, die sich durch einen hohen Gehalt an terminal angeordneten Doppelbindungen auszeichnen. Terminal angeordnete Doppelbindungen sind dabei alpha-olefinische Doppelbindungen des Typs
Besonders geeignete hochreaktive Polyisobutene sind z.B. die Glissopal-Marken der BASF SE, insbesondere Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) und Glissopal 2300 (Mn = 2300) und deren Mischungen. Andere zahlenmittlere Molekulargewichte können nach im Prinzip bekannter Weise durch Mischen von Polyisobutenen unterschiedlicher zahlenmittlerer Molekulargewichte oder durch extraktive Anreicherung von Polyisobutenen bestimmter Molekulargewichtsbereiche eingestellt werden.Particularly suitable highly reactive polyisobutenes are e.g. the Glissopal grades of BASF SE, in particular Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn = 2300) and mixtures thereof. Other number-average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of specific molecular weight ranges.
"Kurzkettiges Hydrocarbyl" oder "niedermolekulares Hydrocarbyl" steht insbesondere für geradkettiges oder verzweigtes Alkyl oder Alkenyl, gegebenenfalls unterbrochen durch eine oder mehrere, wie z.B. 2, 3 oder 4 Heteroatomgruppen, wie -O- oder - NH-. oder gegebenenfalls ein- oder mehrfach, wie z.B. 2, 3 oder 4-fach substituiert."Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" in particular represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally one or more times, e.g. 2, 3 or 4 times substituted.
"Kurzkettiges Hydrocarbyloxy" oder "niedermolekulares Hydrocarbyloxy" steht insbesondere für geradkettiges oder verzweigtes Alkyloxy oder Alkenyloxy, gegebenenfalls unterbrochen durch eine oder mehrere, wie z.B. 2, 3 oder 4 Heteroatomgruppen, wie -O- oder - NH- oder gegebenenfalls ein- oder mehrfach, wie z.B. 2, 3 oder 4-fach substituiert."Short-chain hydrocarbyloxy" or "low molecular weight hydrocarbyloxy" in particular represents straight-chain or branched alkyloxy or alkenyloxy, optionally interrupted by one or more, such as e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH- or optionally mono- or polysubstituted, such as. 2, 3 or 4 times substituted.
"Hydroxysubstituiertes Hydrocarbyl" oder "Hydroxyhydrocarbyl" steht insbesondere für die Hydroxy-substituierten Analoga der hierin definierten Alkyl- oder AlkenylReste."Hydroxysubstituted hydrocarbyl" or "hydroxyhydrocarbyl" refers particularly to the hydroxy-substituted analogs of the alkyl or alkenyl radicals defined herein.
"Alkyl" oder "Niedrigalkyl" steht insbesondere für gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4, 1 bis 6, 1 bis 8, oder 1 bis 10 oder 1 bis 20 Kohlenstoffatomen, wie z. B. Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyl, 1-Ethylpropyl, n-Hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl und 1-Ethyl-2-methylpropyl; sowie n-Heptyl, n-Octyl, n-Nonyl und n-Decyl, sowie die ein- oder mehrfach verzweigten Analoga davon."Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20 carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n -butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n -pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; and n-heptyl, n-octyl, n-nonyl and n-decyl, as well as the mono- or polysubstituted analogs thereof.
"Hydroxyalkyl" steht insbesondere für die ein- oder mehrfach, insbesondere einfach hydroxylierten Analoga obiger Alkylreste, wie z.B. die monohydroxylierten Analoga obiger geradkettiger oder verzweigter Alkylreste, wie z.B. die linearen Hydroxyalkylgruppen mit primärer Hydroxylgruppe, wie Hydroxymethyl, 2-Hydroxyethyl, 3-Hydroxypropyl, 4-Hydroxybutyl."Hydroxyalkyl" is in particular the mono- or polysubstituted, especially monohydricated, analogs of the above-mentioned alkyl radicals, such as, for example, the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, e.g. the linear hydroxyalkyl groups having primary hydroxyl group such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.
"Alkenyl" steht für ein- oder mehrfach, insbesondere einfach ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 4, 2 bis 6, 2 bis 8, 2 bis 10 oder 2 bis 20 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z. B. C2-C6-Alkenyl wie Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-1-propenyl, 2-Methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1 -butenyl, 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl und 1-Ethyl-2-methyl-2-propenyl."Alkenyl" is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 20 carbon atoms and a double bond in any position, for. C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3 Methyl 3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2- propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2 Dimethyl 2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2.2 Dimethyl 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3.3 Dimethyl 2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2 propenyl.
"Hydroxyalkenyl" steht insbesondere für die ein- oder mehrfach, insbesondere einfach hydroxylierten Analoga obiger Alkenylreste"Hydroxyalkenyl" is in particular the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above alkenyl radicals
"Alkyloxy" und "Alkenyloxy" stehen insbesondere für die Sauerstoffverknüpften Analoga abiger "Alkyl" und "Alkeny" -Reste"Alkyloxy" and "alkenyloxy" stand especially for the oxygen-linked analogs of the "alkyl" and "alkeny" radicals
"Alkylen" steht für geradkettige oder ein- oder mehrfach verzweigte Kohlenwasserstoff-Brückengruppen mit 1 bis 10 Kohlenstoffatomen, wie z.B. C1-C7-Alkylengruppen ausgewählt unter -CH2-, -(CH2)2-, -(CH2)3-,-(CH2)4-, -(CH2)2-CH(CH3)-, -CH2-CH(CH3)-CH2- , (CH2)4-, -(CH2)5-, -(CH2)6, -(CH2)7-, -CH(CH3)-CH2-CH2-CH(CH3)- oder - CH(CH3)-CH2-CH2-CH2-CH(CH3)- oder C1-C4-Alkylengruppen ausgewählt unter -CH2-, -(CH2)2-, -(CH2)3-,-(CH2)4-, -(CH2)2-CH(CH3)-, -CH2-CH(CH3)-CH2-; oder für C2-C6-Alkylengruppen, wie z.B. -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CH2-C(CH3)2-, -C(CH3)2-CH(CH3)-, -CH(CH3)-C(CH3)2-, -CH2-CH(Et)-, -CH(CH2CH3)-CH2-, -CH(CH2CH3)-CH(CH2CH3)-, -C(CH2CH3)2-CH2-, -CH2-C(CH2CH3)2-, -CH2-CH(n-Propyl)-, -CH(n-Propyl)-CH2-, -CH(n-Propyl)-CH(CH3)-, -CH2-CH(n-Butyl)-, -CH(n-Butyl)-CH2-, -CH(CH3)-CH(CH2CH3)-, -CH(CH3)-CH(n-Propyl)-, -CH(CH2CH3)-CH(CH3)-, -CH(CH3)-CH(CH2CH3)-, oder für C2-C4-Alkylengruppen, wie z.B. ausgewählt unter -(CH2)2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CH2-C(CH3)2-, -CH2-CH(CH2CH3)-, -CH(CH2CH3)-CH2-,"Alkylene" represents straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as, for example, C 1 -C 7 -alkylene groups selected from -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 2 -CH (CH 3 ) -, -CH 2 -CH (CH 3 ) -CH 2 -, (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or - CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) - or C 1 -C 4 -alkylene groups selected from -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 2 -CH (CH 3 ) -, -CH 2 -CH (CH 3 ) -CH 2 -; or for C 2 -C 6 -alkylene groups, such as -CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH 2 -, -CH (CH 3 ) -CH (CH 3 ) -, -C (CH 3 ) 2 -CH 2 -, -CH 2 -C (CH 3 ) 2 -, -C (CH 3 ) 2 -CH (CH 3 ) -, -CH (CH 3 ) -C (CH 3 ) 2 -, -CH 2 -CH (Et) -, -CH (CH 2 CH 3 ) -CH 2 -, -CH (CH 2 CH 3 ) -CH (CH 2 CH 3 ) -, -C (CH 2 CH 3 ) 2 -CH 2 -, -CH 2 -C (CH 2 CH 3 ) 2 -, -CH 2 -CH (n-propyl) -, -CH (n-propyl) -CH 2 -, -CH (n-) Propyl) -CH (CH 3 ) -, -CH 2 -CH (n-butyl) -, -CH (n-butyl) -CH 2 -, -CH (CH 3 ) -CH (CH 2 CH 3 ) -, -CH (CH 3 ) -CH (n-propyl) -, -CH (CH 2 CH 3 ) -CH (CH 3 ) -, -CH (CH 3 ) -CH (CH 2 CH 3 ) -, or for C C 2 -C 4 -alkylene groups, for example selected from - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH 2 -, -CH (CH 3 ) -CH ( CH 3 ) -, -C (CH 3 ) 2 -CH 2 -, -CH 2 -C (CH 3 ) 2 -, -CH 2 -CH (CH 2 CH 3 ) -, -CH (CH 2 CH 3 ) -CH 2 -,
"Alkenylen" steht für die ein- oder mehrfach, insbesondere einfach ungesättigten Analoga obiger Alkylengruppen mit 2 bis 10 Kohlenstoffatomen, insbesondere für C2-C7-Alkenylene oder C2-C4-Alkenylen, wie -CH=CH-, -CH=CH-CH2-, - CH2-CH=CH-, -CH=CH-CH2-CH2-, -CH2-CH=CH-CH2-, -CH2-CH2-CH=CH-, -CH(CH3)-CH=CH-, -CH2-C(CH3)=CH-."Alkenylene" is the mono- or polysubstituted, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, in particular C 2 -C 7 -alkenylenes or C 2 -C 4 -alkenylene, such as -CH = CH-, -CH = CH-CH 2 -, - CH 2 -CH = CH-, -CH = CH-CH 2 -CH 2 -, -CH 2 -CH = CH-CH 2 -, -CH 2 -CH 2 -CH = CH -, -CH (CH 3 ) -CH = CH-, -CH 2 -C (CH 3 ) = CH-.
"Acyl" steht für Reste abgeleitet von geradkettigen oder verzweigten, gegebenenfalls ein- oder mehrfach ungesättigten, gegebenenfalls substituierten C1-C24-, insbesondere C1-C12- oder C1-C8-Monocarbonsäuren. Beispielsweise sind brauchbare Acylreste abgeleitet von folgenden Carbonsäuren: Gesättigten Säuren , wie Ameisen-, Essig-, Propion- und n- und i-Buttersäure, n- und i-Valeriansäure, Capronsäure, Önanthsäure, Caprylsäure, Pelargonsäure, Caprinsäure, Undecansäure, Laurinsäure, Tridecansäure, Myristinsäure, Pentadecansäure, Palmitinsäure, Margarinsäure, Stearinsäure, Nonadecansäure, Arachinsäure, Behensäure, Lignocerinsäure, Cerotinsäure und Melissinsäure; einfach ungesättigte Säuren, wie Acrylsäure, Crotonsäure, Palmitoleinsäure, Ölsäure und Erucasäure; und zweifach ungesättigten Säuren, wie Sorbinsäure und Linolsäure. Sind in den Fettsäuren Doppelbindungen enthalten, so können diese sowohl in cis- als auch in trans-Form vorliegen."Acyl" is radicals derived from straight-chain or branched, optionally mono- or polyunsaturated, optionally substituted C 1 -C 24 -, in particular C 1 -C 12 - or C 1 -C 8 -monocarboxylic acids. For example, useful acyl radicals are derived from the following carboxylic acids: saturated acids such as formic, acetic, propionic and n- and i-butyric acid, n- and i-valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, Tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, behenic, lignoceric, cerotic and melissic acids; monounsaturated acids such as acrylic acid, crotonic acid, palmitoleic acid, oleic acid and erucic acid; and diunsaturated acids such as sorbic acid and linoleic acid. If double bonds are present in the fatty acids, these may be in both cis and trans form.
"Zyklische Hydrocarbylreste" umfassen insbesondere:
- Cycloalkyl: carbocyclische Reste mit 3 bis 20 Kohlenstoffatomen, wie z.B. C3-C12-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl, Cycloheptyl, sowie Cyclopropyl-methyl, Cyclopropyl-ethyl, Cyclobutyl-methyl, Cyclobutyl-ethyl, Cyclopentyl-methyl, Cyclopentyl-ethyl, Cyclohexyl-methyl oder C3-C7-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclopropyl-methyl, Cyclopropyl-ethyl, Cyclobutyl-methyl, Cyclopentyl-ethyl, Cyclohexyl-methyl, wobei die Anbindung an den Rest des Moleküls über jegliches geeignetes C-Atom erfolgen kann.
- Cycloalkenyl: monocyclische, einfach ungesättigte Kohlenwasserstoffgruppen mit 5
bis 8,vorzugsweise bis 6 Kohlenstoffringgliedern, wie Cyclopenten-1-yl, Cyclopenten-3-yl, Cyclohexen-1-yl, Cyclohexen-3-yl und Cyclohexen-4-yl; - Aryl: ein- oder mehrkernige, vorzugsweise ein- oder zweikernige, gegebenenfalls substituierte aromatische Reste
mit 6 bis 20 wie z.B. 6bis 10 Ring-Kohlenstoffatomen, wie z.B. Phenyl, Biphenyl, Naphthyl wie 1- oder 2-Naphthyl, Tetrahydronaphthyl, Fluorenyl, Indenyl und Phenanthrenyl. Diese Arylreste können gegebenenfalls 1, 2, 3, 4, 5oder 6 gleiche oder verschiedene Substituenten tragen. - Arylalkyl: die Aryl-substituierten Analoga obiger Alkylreste, wobei Aryl ebenfalls die oben angegebenen Bedeutungen besitzt, wie z.B. Phenyl-C1-C4-Alkylreste ausgewählt unter Phenyl-methyl oder Phenyl-ethyl.
- Heterocyclyl: fünf- bis siebengliedrige gesättigte, partiell ungesättigte oder aromatische(= Heteroaryl bzw. Hetaryl) Heterocyclen bzw. Heterocyclylreste, enthaltend ein, zwei , drei oder vier Heteroatome aus der Gruppe O, N oder S. Beispielsweise können folgende Untergruppen genannt werden
- 5- oder 6-gliedriges gesättigtes oder einfach ungesättigtes Heterocyclyl, enthaltend ein bis zwei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome als Ringglieder, z. B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 1-Pyrrolidinyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-Isoxazolidinyl, 4-Isoxazolidinyl, 5-Isoxazolidinyl, 3-Isothiazolidinyl, 4-Isothiazolidinyl, 5-Isothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thiazolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-Imidazolidinyl, 4-Imidazolidinyl, 2-Pyrrolin-2-yl, 2-Pyrrolin-3-yl, 3-Pyrrolin-2-yl, 3-Pyrrolin-3-yl, 1-Piperidinyl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 1,3-Dioxan-5-yl, 2-Tetrahydropyranyl, 4-Tetrahydropyranyl, 2-Tetrahydrothienyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl und 2-Piperazinyl;
- 5-gliedriges aromatisches Heterocyclyl, enthaltend neben Kohlenstoffatomen ein, zwei oder drei Stickstoffatome oder ein oder zwei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder, z. B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 2-Imidazolyl, 4-Imidazolyl, und 1,3,4-Triazol-2-yl;
- 5-gliedriges aromatisches Heterocyclyl,
das 1, 2, 3oder 4 Stickstoffatome als Ringglieder aufweist, wie 1-, 2- oder 3-Pyrrolyl, 1-, 3- oder 4-Pyrazolyl, 1-, 2- oder 4-Imidazolyl, 1,2,3-[1H]-Triazol-1-yl, 1,2,3-[2H]-Triazol-2-yl, 1,2,3-[1H]-Triazol-4-yl, 1,2,3-[1H]-Triazol-5-yl, 1,2,3-[2H]-Triazol-4-yl, 1,2,4-[1H]-Triazol-1-yl, 1,2,4-[1H]-Triazol-3-yl, 1,2,4-[1H]-Triazol-5-yl, 1,2,4-[4H]-Triazol-4-yl, 1,2,4-[4H]-Triazol-3-yl, [1H]-Tetrazol-1-yl, [1H]-Tetrazol-5-yl, [2H]-Tetrazol-2-yl und [2H]-Tetrazol-5-yl; - 5-gliedriges aromatisches Heterocyclyl, das 1 unter Sauerstoff und Schwefel ausgewähltes Heteroatome und gegebenenfalls 1, 2 oder 3 Stickstoffatome als Ringglieder aufweist, beispielsweise 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 3- oder 4-Isoxazolyl, 3- oder 4- Isothiazolyl, 2-, 4- oder 5-Oxazolyl, 2-, 4 oder 5-Thiazolyl, 1,2,4-Thiadiazol-3-yl, 1,2,4-Thiadiazol-5-yl, 1,3,4-Thiadiazol-2-yl, 1,2,4-Oxadiazol-3-yl, 1,2,4-Oxadiazol-5-yl und 1,3,4-Oxadiazol-2-yl;
- 6-gliedriges Heterocyclyl, enthaltend neben Kohlenstoffatomen ein oder zwei bzw. ein, zwei oder drei Stickstoffatome als Ringglieder, z. B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl, 2-Pyrazinyl, 1,2,4-Triazin-3-yl; 1,2,4-Triazin-5-yl, 1,2,4-Triazin-6-yl und 1,3,5-Triazin-2-yl;
- Cycloalkyl: carbocyclic radicals having from 3 to 20 carbon atoms, such as, for example, C 3 -C 12 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl, cycloheptyl and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C 3 -C 7 -cycloalkyl, such as cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, wherein the attachment to the rest of the molecule via any suitable carbon atom can take place.
- Cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having from 5 to 8, preferably to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;
- Aryl: mononuclear or polynuclear, preferably mononuclear or dinuclear, optionally substituted aromatic radicals having 6 to 20 such as 6 to 10 ring carbon atoms, such as phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl and phenanthrenyl. These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents.
- Arylalkyl: the aryl-substituted analogs of the above alkyl radicals, wherein aryl likewise has the abovementioned meanings, such as, for example, phenyl-C 1 -C 4 -alkyl radicals selected from phenylmethyl or phenylethyl.
- Heterocyclyl: five to seven-membered saturated, partially unsaturated or aromatic (= heteroaryl or hetaryl) heterocycles or heterocyclyl radicals containing one, two, three or four heteroatoms from the group O, N or S. For example, the following subgroups may be mentioned
- 5- or 6-membered saturated or monounsaturated heterocyclyl containing one to two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, for. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2- Pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1.3- Dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
- 5-membered aromatic heterocyclyl containing, in addition to carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl;
- 5-membered aromatic heterocyclyl having 1, 2, 3 or 4 nitrogen atoms as ring members, such as 1-, 2- or 3-pyrrolyl, 1-, 3- or 4-pyrazolyl, 1-, 2- or 4-imidazolyl, 1,2,3- [1H] -triazol-1-yl, 1,2,3- [2H] -triazol-2-yl, 1,2,3- [1H] -triazol-4-yl, 1, 2,3- [1H] -triazol-5-yl, 1,2,3- [2H] -triazol-4-yl, 1,2,4- [1H] -triazol-1-yl, 1,2, 4- [1H] -triazol-3-yl, 1,2,4- [1H] -triazol-5-yl, 1,2,4- [4H] -triazol-4-yl, 1,2,4- [4H] -triazol-3-yl, [1H] -tetrazol-1-yl, [1H] -tetrazol-5-yl, [2H] -tetrazol-2-yl, and [2H] -tetrazol-5-yl;
- 5-membered aromatic heterocyclyl which has 1 heteroatom selected from oxygen and sulfur and optionally 1, 2 or 3 nitrogen atoms as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3- or 4-isoxazolyl, 3- or 4- isothiazolyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl;
- 6-membered heterocyclyl containing in addition to carbon atoms one or two or one, two or three nitrogen atoms as ring members, for. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,2,4-triazin-3-yl; 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl and 1,3,5-triazin-2-yl;
"Substituenten" für hierin angegebene Reste, sind insbesondere ausgewählt sind unter Ketogruppen, - COOH, -COO-Alkyl, - OH, -SH, -CN, Amino, -NO2, Alkyl, oder Alkenylgruppen."Substituents" for radicals specified herein are especially selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups.
Das eingesetzte Anhydrid ist von beliebigen, aliphatischen zwei- oder mehrwertigen (wie z.B. 3- oder- 4 wertig), insbesondere von Di-, Tri- oder Tetracarbonsäuren abgeleitet, und gegebenenfalls durch einen oder mehrere (wie z.B. 2 oder 3), insbesondere einem langkettigen Alkylrest und/oder einem hochmolekularen Hydrocarbylrest, insbesondere einem Polyalkylenrest substituiert. Beispiele sind Anhydride von C3 - C10 Polycarbonsäuren, wie die Dicarbonsäuren Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Suberinsäure, Azelainsäure und Sebacinsäure, und deren verzweigte Analoga; sowie die Tricarbonsäure Citronensäure. Die Anhydride können auch aus den entsprechenden einfach ungesättigten Säuren und Addition wenigstens eines langkettigen Alkylrests und/oder hochmolekularen Hydrocarbylrests erzeugt werden. Beispiele geeigneter einfach ungesättigter Säuren sind Fumarsäure, Maleinsäure, Itaconsäure.The anhydride used is derived from any aliphatic di- or polyvalent (such as 3- or 4-valent), in particular of di-, tri- or tetracarboxylic, and optionally by one or more (such as 2 or 3), in particular one long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical substituted. Examples are anhydrides of C 3 -C 10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid. The anhydrides can also be generated from the corresponding monounsaturated acids and addition of at least one long chain alkyl group and / or high molecular weight hydrocarbyl group. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.
Der hydrophobe "langkettige" oder" hochmolekulare" Hydrocarbylrest, welcher für die ausreichende Löslichkeit des quaternisierten Produkts im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, wie z.B. 113 bis 10.000, oder 200 bis 10.000 oder 350 bis 5.000, wie z.B. 350 bis 3.000, 500 bis 2.500, 700 bis 2.500, oder 800 bis 1.500. Als typische hydrophobe Hydrocarbylreste sind zu nennen Polypropenyl-, Polybutenyl- und Polyisobutenylreste, z.B. mit einem zahlenmittleren Molekulargewicht Mn von 3.500 bis 5.000, 350 bis 3.000, 500 bis 2.500, 700 bis 2.500 und 800 bis 1.500.The hydrophobic "long chain" or "high molecular weight" hydrocarbyl moiety which provides sufficient solubility of the quaternized product in the fuel has a number average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000 such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500. Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example having a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.
Geeignete Hydrocarbyl substituierte Anhydride sind z.B. beschrieben in der
Geeignete Hydrocarbyl-substituierte Polycarbonsäureanhydride umfassen auch polymere, insbesondere dimere Formen solcher Hydrocarbyl-substituierten Polycarbonsäureanhydride. Dimere Formen enthalten insbesondere zwei Säureanhydridgruppen welche unabhängig voneinander im erfindungsgemäßen Herstellungsverfahren mit der quaternisierbaren Stickstoffverbindung umgesetzt werden können.Suitable hydrocarbyl-substituted polycarboxylic acid anhydrides also include polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid anhydrides. In particular, dimeric forms contain two acid anhydride groups which can be reacted independently of one another in the preparation process according to the invention with the quaternizable nitrogen compound.
Als Quaternisierungsmittel kommen im Prinzip alle als solche geeigneten Verbindungen in Betracht. In einer besonderen Ausführungsform erfolgt die Quaternisierung des mindestens einen quaternisierbaren tertiären Stickstoffatoms jedoch mit mindestens einem Quaternisierungsmittel ausgewählt aus Epoxiden, insbesondere Hydrocarbyl-Epoxiden.
Als Hydrocarbyl-Epoxide eignen sich beispielsweise aliphatische und aromatische Alkylenoxide, wie insbesondere C2-12-Alkylenoxide, wie Ethylenoxid, Propylenoxid, 1,2-Butylenoxid, 2,3-Butylenoxid, 2-Methyl-1,2-propenoxid (Isobutenoxid), 1,2-Pentenoxid, 2,3-Pentenoxid, 2-Methyl-1,2-butenoxid, 3-Methyl-1,2-butenoxid, 1,2-Hexenoxid, 2,3-Hexenoxid, 3,4-Hexenoxid, 2-Methyl-1,2-pentenoxid, 2-Ethyl-1,2-butenoxid, 3-Methyl-1,2-pentenoxid, 1,2-Decenoxid, 1,2-Dodecenoxid oder 4-Methyl-1,2-pentenoxid; sowie aromatensubstituierte Ethylenoxide, wie gegebenenfalls substituiertes Styroloxid, insbesondere Styroloxid oder 4-Methyl-styroloxid.Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-12 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide). , 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide , 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2 -pentenoxid; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene oxide.
Im Falle der Verwendung von Epoxiden als Quaternisierungsmittel werden diese insbesondere in Abwesenheit von freien Säuren, insbesondere in Abwesenheit von freien Protonensäuren, wie vor allem von C1-12-Monocarbonsäuren, wie Ameisensäure, Essigsäure oder Propionsäure oder C2-12-Dicarbonsäuren wie Oxalsäure oder Adipinsäure; oder auch in Abwesenheit von Sulfonsäuren, wie Benzolsulfonsäure oder Toluolsulfonsäure oder wässrigen Mineralsäuren, wie Schwefelsäure oder Salzsäure, eingesetzt. Das so hergestellte Quaternisierungsprodukt ist damit "säurefrei" im Sinne der vorliegenden Erfindung.In the case of the use of epoxides as quaternizing these are especially in the absence of free acids, especially in the absence of free protic acids, especially of C 1-12 monocarboxylic acids such as formic acid, acetic acid or propionic acid or C 2-12 dicarboxylic acids such as oxalic acid or adipic acid; or in the absence of sulfonic acids, such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids, such as sulfuric acid or hydrochloric acid. The quaternization product thus produced is thus "acid-free" within the meaning of the present invention.
Die mit dem Anhydrid reaktive, quaternisierbare Stickstoff-Verbindung ist ausgewählt unter
- a. Hydroxyalkyl-substituierten Mono- oder Polyaminen mit wenigstens einer quarternisierten (z.B. Cholin) oder quaternisierbaren, primären, sekundären oder tertiären Aminogruppe,
- b. geradkettigen oder verzweigtem, cyclischen, heterocyclischen, aromatischen oder nichtaromatischen Polyaminen mit wenigstens einer primären oder sekundären (anhydridreaktiven) Aminogruppe und mit wenigstens einer quarternisierten oder quaternisierbaren, primären, sekundären oder tertiären Aminogruppe;
- c. Piperazinen.
- a. Hydroxyalkyl-substituted mono- or polyamines having at least one quaternized (eg choline) or quaternizable, primary, secondary or tertiary amino group,
- b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quaternizable, primary, secondary or tertiary amino group;
- c. Piperazines.
Insbesondere ausgewählt sind die quaternisierbaren Stickstoff-Verbindung unter
- a. Hydroxyalkyl-substituierten primären, sekundären, tertiären oder quartären Monoaminen und Hydroxyalkyl-substituierten primären, sekundären, tertiären oder quartären Diaminen.
- b. geradkettigen oder verzweigten aliphatischen Diaminen mit zwei primären Aminogruppen; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer sekundären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer tertiären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer quartären Aminogruppe; aromatischen carbo-cyclischen Diaminen mit zwei primären Aminogruppen; aromatischen heterocyclischen Polyaminen mit zwei primären Aminogruppen; aromatischen oder nichtaromatischen Heterozyklen mit einer primären und einer tertiären Aminogruppe;
- a. Hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.
- b. straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; Di- or polyamines having at least one primary and at least one quaternary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group;
Beispiele für geeignete "hydroxyalkyl-substituierte Mono- oder Polyamine" sind solche die mit wenigstens einem, wie z.B. 1, 2, 3, 4, 5 oder 6, Hydroxyalkyl-Substituenten ausgestattet sind.Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those containing at least one, e.g. 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents are equipped.
Ala Beispiele für "Hydroxyalkyl-substituierte Monoamine" können genannt werden: N-Hydroxyalkyl-monoamine, N,N-Dihydroxyalkyl-monoamine und N,N,N-Trihydroxyalkyl-monoamine, wobei die Hydroxyalkylgruppen gleich oder verschieden sind und außerdem wie oben definiert sind. Hydroxyalkyl steht dabei insbesondere für 2-Hydroxyethyl, 3-Hydroxypropyl oder 4-Hydroxybutyl.Ala examples of "hydroxyalkyl-substituted monoamines" may be mentioned: N-hydroxyalkyl-monoamines, N, N-dihydroxyalkyl-monoamines and N, N, N-trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above , Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
Beispielsweise können folgende "Hydroxyalkyl-substituierte Polyamine" und insbesondere "Hydroxyalkyl-substituierte Diamine" genannt werden: (N-Hydroxyalkyl)-alkylendiamine, N,N-Dihydroxyalkyl-alkylendiamine, wobei die Hydroxyalkylgruppen gleich oder verschieden sind und außerdem wie oben definiert sind. Hydroxyalkyl steht dabei insbesondere für 2-Hydroxyethyl, 3-Hydroxypropyl oder 4-Hydroxybutyl; Alkylen steht dabei insbesondere für Ethylen, Propylen oder Butylen.For example, the following "hydroxyalkyl-substituted polyamines" and especially "hydroxyalkyl-substituted diamines" may be mentioned: (N-hydroxyalkyl) -alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Alkylene stands in particular for ethylene, propylene or butylene.
Geeignete "Diamine" sind Alkylendiamine, sowie die N-alkylsubstituierten Analoga davon, wie N-monoalkylierten Alkylendiamine und die N,N- oder N, N' -dialkylierten Alkylendiamine. Alkylen steht insbesondere für geradkettiges oder verzweigtes C1-7 oder C1-4-Alkylen, wie oben definiert. Alkyl steht insbesondere für C1-4-Alkyl gemäß obiger Definition. Beispiele sind insbesondere Ethylendiamin, 1,2-Propylendiamin, 1,3-Propylendiamin, 1,4-Butylendiamin und Isomere davon, Pentandiamin und Isomere davon, Hexandiamin und Isomere davon, Heptandiamin und Isomere davon, sowie ein- oder mehrfach, wie z.B. ein- oder zweifach C1-C4-alkylierte, wie z.B. methylierte, Derivate der vorher genannten Diamin-Verbindungen, wie z.B. 3-Dimethylamino-1-propylamin (DMAPA), N,N-Diethylaminopropylamin, und N,N-Dimethylaminoethylamin.Suitable "diamines" are alkylenediamines, as well as the N-alkyl substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N, N or N, N'-dialkylated alkylenediamines. Alkylene in particular represents straight-chain or branched C 1-7 or C 1-4 -alkylene, as defined above. Alkyl is in particular C 1-4 -alkyl as defined above. Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and one or more times, such as a or C 1 -C 4 -alkylated, such as methylated, derivatives of the aforementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA), N, N-diethylaminopropylamine, and N, N-dimethylaminoethylamine.
Geeignete geradkettige "Polyamine" sind beispielsweise Dialkylentriamin, Trialkylentetramin, Tetraalkylenpentamin, Pentaalkylenhexamin, sowie die N-alkylsubstituierten Analoga davon, wie N-monoalkylierten und die N,N- oder N, N' - dialkylierten Alkylenpolyamine. Alkylen steht insbesondere für geradkettiges oder verzweigtes C1-7 oder C1-4-Alkylen, wie oben definiert. Alkyl steht insbesondere für C1-4-Alkyl gemäß obiger Definition.Suitable straight-chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N, N or N, N'-dialkylated Alkylenpolyamine. Alkylene in particular represents straight-chain or branched C 1-7 or C 1-4 -alkylene, as defined above. Alkyl is in particular C 1-4 -alkyl as defined above.
Beispiele sind insbesondere Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin, Dipropylentriamin, Tripropylenetetramin, Tetrapropylenpentamin, Pentapropylenhexamin, Dibutylentriamin, Tributylentetramin, Tetrabutylenpentamin, Pentabutylenhexamin; sowie die N,N-Dialkylderivate davon, insbesondere die N,N-Di-C1-4-alkylderivate davon. Als Beispiele können genannt werden: N,N-Dimethyldimethylentriamin, N,N-Diethyldimethylentriamin, N,N-Dipropyldimethylentriamin, N,N-Dimethyldiethylen-1,2-triamin, N,N-Diethyldiethylen-1,2-triamin, N,N-Dipropyldiethylen-1,2-triamin, N,N-Dimethyldipropylen-1,3-triamin (i.e. DMAPAPA), N,N-Diethyldipropylen-1,3-triamin, N,N-Dipropyldipropylen-1,3-triamin, N,N-Dimethyldibutylen-1,4-triamin, N,N-Diethyldibutylen-1,4-triamin, N,N-Dipropyldibutylen-1,4-triamin, N,N-Dimethyldipentylen-1,5-triamin, N,N-Diethyldipentylen-1,5-triamin, N,N-Dipropyldipentylen-1,5-triamin, N,N-Dimethyldihexylen-1,6-triamin, N,N-Diethyldihexylen-1,6-triamin und N,N-Dipropyldihexylen-1,6-triamin,Examples are in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenhexamine; and the N, N-dialkyl derivatives thereof, especially the N, N-di-C 1-4 alkyl derivatives thereof. Examples which may be mentioned are: N, N-dimethyldimethylenetriamine, N, N-diethyldimethylenetriamine, N, N-dipropyldimethylenetriamine, N, N-dimethyldiethylene-1,2-triamine, N, N-diethyldiethylene-1,2-triamine, N, N-dipropyldiethylene-1,2-triamine, N, N-dimethyl-dipropylene-1,3-triamine (ie DMAPAPA), N, N-diethyl-dipropylene-1,3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyldibutylene-1,4-triamine, N, N-diethyldibutylene-1,4-triamine, N, N-dipropyldibutylene-1,4-triamine, N, N-dimethyldipentylene-1,5-triamine, N, N-Diethyldipentylen-1,5-triamine, N, N-dipropyldipentylene-1,5-triamine, N, N-dimethyldihexylene-1,6-triamine, N, N-diethyldihexylene-1,6-triamine and N, N-dipropyldihexylene-1,6-triamine;
"Aromatische carbocyclischen Diamine" mit zwei primären Aminogruppen sind die di-aminosubstituierten Derivate von Benzol, Biphenyl, Naphthalin, Tetrahydronaphthalin, Fluoren, Inden und Phenanthren."Aromatic carbocyclic diamines" having two primary amino groups are the di-amino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene, and phenanthrene.
"Aromatische oder nicht-aromatische heterocyclische Polyamine" mit zwei primären Aminogruppen sind die mit zwei Aminogruppen substituierten Derivate von folgenden Heterocyclen:;
- 5- oder 6-gliedriges gesättigtes oder einfach ungesättigtes Heterocyclen, enthaltend ein bis zwei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome als Ringglieder, z. B. Tetrahydrofuran, Pyrrolidin, Isoxazolidin, Isothiazolidin, Pyrazolidin, Oxazolidin, Thiazolidin, Imidazolidin, Pyrrolin, Piperidin, Piperidinyl, 1,3-Dioxan, Tetrahydropyran, Hexahydropyridazin, Hexahydropyrimidin, Piperazin;
- 5-gliedrige aromatische Heterocyclen, enthaltend neben Kohlenstoffatomen ein, zwei oder drei Stickstoffatome oder ein oder zwei Stickstoffatome und ein Schwefel- oder Sauerstoffatom als Ringglieder, z. B. Furan, Thian, Pyrrol, Pyrazol, Oxazol, Thiazol, Imidazol und 1,3,4-Triazol; Isoxazol, Isothiazol, Thiadiazol, Oxadiazol
- 6-gliedrige Heterocyclen enthaltend neben Kohlenstoffatomen ein oder zwei bzw. ein, zwei oder drei Stickstoffatome als Ringglieder, z. B. Pyridinyl,Pyridazin, Pyrimidin, Pyrazinyl, 1,2,4-Triazin , 1,3,5-Triazin-2-yl;
- 5- or 6-membered saturated or monounsaturated heterocycles containing one to two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, eg. Tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1,3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine;
- 5-membered aromatic heterocycles containing, in addition to carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, e.g. Furan, thian, pyrrole, pyrazole, oxazole, thiazole, imidazole and 1,3,4-triazole; Isoxazole, isothiazole, thiadiazole, oxadiazole
- 6-membered heterocycles containing in addition to carbon atoms one or two or one, two or three nitrogen atoms as ring members, for. Pyridinyl, pyridazine, pyrimidine, pyrazinyl, 1,2,4-triazine, 1,3,5-triazin-2-yl;
"Aromatische oder nichtaromatische Heterozyklen mit einer primären und einer tertiären Aminogruppe" sind beispielsweise die oben genannten N-Heterocyclen, welche an wenigstens einem Ring-N-Atom aminoalkyliert sind, und insbesondere eine Amino-C1-4-alkylgruppe tragen."Aromatic or non-aromatic heterocycles having a primary and a tertiary amino group" are, for example, the abovementioned N-heterocycles, which are aminoalkylated on at least one ring N atom, and in particular carry an amino-C 1-4 -alkyl group.
"Aromatischen oder nichtaromatischen Heterozyklen mit einer tertiären Aminogruppe und einer Hydroxyalkylgruppe" sind beispielsweise die oben genannten N-Heterocyclen, welche an wenigstens einem Ring-N-Atom hydroxyalkyliert sind, und insbesondere eine Hydroxy-C1-4-alkylgruppe tragen."Aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group" are, for example, the abovementioned N-heterocycles, which are hydroxyalkylated on at least one ring N-atom, and in particular a hydroxy-C 1-4 alkyl group.
Folgende Gruppen einzelner Verbindungsklassen quaternisierbarer Stickstoffverbindungen seien insbesondere genannt:
Die Umsetzung der Hydrocarbyl-substituierten Polycarbonsäureanhydrid-Verbindung mit der quaternisierbaren Stickstoffverbindung erfolgt unter thermisch kontrollierten Bedingungen, so dass im Wesentlichen keine Kondensationsreaktion erfolgt. Insbesondere ist erfindungsgemäß keine Bildung von Reaktionswasser zu beobachten. Insbesondere erfolgt die Reaktion bei einer Temperatur im Bereich von 10 bis 80, insbesondere 20 bis 60 oder 30 bis 50 °C. Die Reaktionsdauer kann dabei im Bereich von wenigen Minuten oder einigen Stunden, wie z.B. etwa 1 Minute bis zu etwa 10 Stunden liegen. Der Umsetzung kann dabei bei etwa 0,1 bis 2 atm Druck, insbesondere aber etwa bei Normaldruck erfolgen. Insbesondere ist eine Inertgas-Atmosphäre, wie z.B. Stickstoff, zweckmäßig.The reaction of the hydrocarbyl-substituted polycarboxylic anhydride compound with the quaternizable nitrogen compound takes place under thermally controlled conditions, so that essentially no condensation reaction takes place. In particular, according to the invention, no formation of water of reaction can be observed. In particular, the reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 ° C. The reaction time can be in the range of a few minutes or a few hours, such as about 1 minute to about 10 hours. The reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure. In particular, an inert gas atmosphere, such as nitrogen, is useful.
Die Reaktanden werden insbesondere in etwa äquimolaren Mengen vorgelegt, gegebenenfalls ist ein geringer, z. B. 0,05 bis 0,5-facher, wie z.B. 0,1 bis 0,3 facher, molarer Überschuss des Anhydrids wünschenswert. Falls erforderlich können die Reaktanden in einem geeigneten inerten organischen aliphatischen oder aromatischen Lösungsmittel oder einem Gemisch davon, vorgelegt werden. Typischen Beispiele sind z.B. Lösungsmittel der Solvesso Serie, Toluol oder Xylol. Gemäß einer weiteren besonderen Ausführungsform wird die Umsetzung aber in Abwesenheit von organischen Lösungsmittel, insbesondere protischen Lösungsmitteln, durchgeführt.The reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. 0.05 to 0.5 times, e.g. 0.1 to 0.3 fold, molar excess of the anhydride desirable. If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are e.g. Solvesso series solvent, toluene or xylene. According to a further particular embodiment, however, the reaction is carried out in the absence of organic solvents, in particular protic solvents.
Bei erfindungsgemäßer Durchführung der Umsetzung erfolgt die Ringöffnung des Anhydrids unter Addition der quaternisierbaren Stickstoffverbindung über deren reaktive Sauerstoff oder Stickstoffgruppe (wie z.B. Hydroxylgruppe oder primäre oder sekundäre Amingruppe) und ohne die Abspaltung von Kondensationswasser. Das dabei anfallende Reaktionsprodukt umfasst eine Polycarbonsäure-Zwischenprodukt, mit wenigstens einer neugebildeten Säureamidgruppe bzw. Estergruppe und wenigstens einer intramolekularen, gebundenen, neu gebildeten Carbonsäure- bzw. Carboxylatgruppe, in stöchiometrischem Anteil zu der durch die Additionsreaktion intramolekular gebundenen quaternisierbaren Aminogruppe.In carrying out the reaction according to the invention, the ring opening of the anhydride is carried out with addition of the quaternizable nitrogen compound via its reactive oxygen or nitrogen group (such as hydroxyl group or primary or secondary amine group) and without the elimination of water of condensation. The resulting reaction product comprises a polycarboxylic acid intermediate, with at least one newly formed acid amide or ester group and at least one intramolecular, bound, newly formed carboxylic acid or carboxylate group, in stoichiometric proportion to the intramolecularly bound by the addition reaction quaternizable amino group.
Das so gebildete Reaktionsprodukt kann theoretisch weiter aufgereinigt oder das Lösungsmittel entfernt werden. Gewöhnlich ist dies aber nicht zwingend notwendig, so dass das Reaktionsprodukt ohne weitere Aufreinigung in den nächsten Syntheseschritt, der Quaternisierung, überführt werden kann.The reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.
Die Epoxid-basierte Quaternisierung gemäß Reaktionsschritt (b) wird nun in völliger Abkehr von bisher beschriebenen Methoden des Standes der Technik ohne Säurezusatz durchgeführt. Der durch Aminaddition gebildete Carboxylrest unterstützt dabei die Epoxid-Ringöffnung und damit die Quaternisierung der Aminogruppe. Das dabei anfallende Reaktionsprodukt weist somit kein freies Säureanion auf. Das Produkt ist dennoch aufgrund seiner Betain-Struktur ladungsneutral.The epoxide-based quaternization according to reaction step (b) is now carried out in complete departure from previously described methods of the prior art without addition of acid. The carboxyl radical formed by amine addition supports the epoxide ring opening and thus the quaternization of the amino group. The resulting Reaction product thus has no free acid anion. Nevertheless, the product is charge-neutral due to its betaine structure.
Zur Durchführung der Quaternisierung versetzt man das Reaktionsprodukt oder Reaktionsgemisch aus Stufe a) mit wenigstens einer Epoxidverbindung obiger Formel (II), insbesondere in den erforderlichen stöchiometrischen Mengen, um die gewünschte Quaternisierung zu erreichen. Pro Äquivalent an quaternisierbarem tertiären Stickstoffatom kann man z.B. 0,1 bis 1,5 Äquivalente, oder 0,5 bis 1,25 Äquivalente, an Quaternisierungsmittel einsetzen. Insbesondere werden aber etwa annähernd äquimolare Anteile des Epoxids eingesetzt, um eine tertiäre Amingruppe zu quaternisieren. Entsprechend höhere Einsatzmengen sind erforderlich, um eine sekundäre oder primäre Amingruppe zu quaternisieren.To carry out the quaternization, the reaction product or reaction mixture from stage a) is mixed with at least one epoxide compound of the above formula (II), in particular in the required stoichiometric amounts, in order to achieve the desired quaternization. Per equivalent of quaternizable tertiary nitrogen atom can be e.g. 0.1 to 1.5 equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent. In particular, however, approximately equimolar amounts of the epoxide are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group.
Man arbeitet hierbei typischerweise bei Temperaturen im Bereich von 15 bis 90°C, insbesondere von 20 bis 80 oder 30 bis 70 °C. Die Reaktionsdauer kann dabei im Bereich von wenigen Minuten oder einigen Stunden, wie z.B. etwa 10 Minuten bis zu etwa 24 Stunden liegen. Der Umsetzung kann dabei bei etwa 0,1 bis 20 bar, wie z.B. 1 bis 10 oder 1,5 bis 3 bar Druck, insbesondere aber etwa bei Normaldruck erfolgen. Insbesondere ist eine Inertgas-Atmosphäre, wie z.B. Stickstoff, zweckmäßig.In this case, one typically works at temperatures in the range of 15 to 90 ° C, in particular from 20 to 80 or 30 to 70 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 10 minutes to about 24 hours. The reaction may be carried out at about 0.1 to 20 bar, e.g. 1 to 10 or 1.5 to 3 bar pressure, but especially at about atmospheric pressure. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.
Falls erforderlich können die Reaktanden in einem geeigneten inerten organischen aliphatischen oder aromatischen Lösungsmittel oder einem Gemisch davon, für die Epoxidierung vorgelegt werden, oder es ist noch eine ausreichender Anteil an Lösungsmittel aus Reaktionsschritt a) vorhanden. Typischen Beispiele sind z.B. Lösungsmittel der Solvesso Serie, Toluol oder Xylol. Gemäß einer weiteren besonderen Ausführungsform wird die Umsetzung aber in Abwesenheit von organischen Lösungsmittel, insbesondere protischen (organischen) Lösungsmitteln, durchgeführt.If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof for epoxidation, or there may still be a sufficient amount of solvent from reaction step a). Typical examples are e.g. Solvesso series solvent, toluene or xylene. According to a further particular embodiment, the reaction is carried out in the absence of organic solvents, in particular protic (organic) solvents.
"Protische Lösungsmittel" , welche erfindungsgemäß insbesondere keine Anwendung finden, sind insbesondere solche, mit einer Dielektrizitätskonstante von größer als 9. Derartige protische Lösungsmittel enthalten gewöhnlich wenigstens eine HO-Gruppe und können zudem wasserhaltig sein. Typische Beispiele sind z.B. Glycole und Glycolether sowie Alkohole, wie aliphatische, cyclisch-aliphatische, aromatische oder heterocyclische Alkohole."Protic solvents" which in particular are not used according to the invention are, in particular, those having a dielectric constant of greater than 9. Such protic solvents usually contain at least one HO group and can also be hydrous. Typical examples include glycols and glycol ethers and alcohols, such as aliphatic, cyclic-aliphatic, aromatic or heterocyclic alcohols.
Das so gebildete Reaktionsendprodukt kann theoretisch weiter aufgereinigt oder das Lösungsmittel kann entfernt werden. Gewöhnlich ist dies aber nicht zwingend notwendig, so dass das Reaktionsprodukt ohne weitere Aufreinigung als Additiv, gegebenenfalls nach Abmischung mit weiteren Additivkomponenten (s. unten) einsetzbar ist, zumal ja auch keine korrosiv wirkenden, freien Protonensäuren im Reaktionsprodukt enthalten sind.The final reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below), especially since no corrosive, free protic acids are contained in the reaction product.
Als nichtlimitierendes Beispiel für die Umsetzung einer Polyalkylensubstituierten Dicarbonsaäureanhydrid-Verbindung durch Amin-Addition bzw. Alkohol-Addition und anschließende Quaternisierung sei auf folgende beispielhafte Reaktionsschemata verwiesen, worin R1 bis R7, L1 und L2 obige Bedeutungen besitzen:
- Stufe 1: Herstellung des substituierten Dicarbonsäureanhydrids
- Stufe 2a: Aminierung und Quaternisierung
- Stufe 2b: Esterbildung und Quaternisierung
- Step 1: Preparation of the substituted dicarboxylic acid anhydride
- Step 2a: Amination and Quaternization
- Step 2b: Ester formation and quaternization
Der mit dem erfindungsgemäßen quaternisierten Additiv additivierte Kraftstoff ist ein Ottokraftstoff oder insbesondere ein Mitteldestillat-Kraftstoff, vor allem ein Dieselkraftstoff.The fuel additized with the quaternized additive according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel.
Der Kraftstoff kann weitere übliche Additive zur Wirksamkeitsverbesserung und/oder Verschleißunterdrückung enthalten.The fuel may contain other conventional additives to improve the effectiveness and / or wear suppression.
Im Falle von Dieselkraftstoffen sind dies in erster Linie übliche Detergens-Additive, Trägeröle, Kaltfließverbesserer, Schmierfähigkeitsverbesserer (Lubricity Improver), Korrosionsinhibitoren, Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or Solvent.
Im Falle von Ottokraftstoffen sind dies vor allem Schmierfähigkeitsverbesserer (Friction Modifier), Korrosionsinhibitoren, Demulgatoren, Dehazer, Antischaummittel, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel.In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
Typische Beispiele geeigneter Co-Additive sind im folgenden Abschnitt aufgeführt:
- B1) Detergens-Additive
- B1) detergent additives
Vorzugsweise handelt es sich bei den üblichen Detergens-Additiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20.000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:
- (Da) Mono- oder Polyaminogruppen
mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat; - (Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
- (Dc) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
- (Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
- (Df) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
- (Dg) Carbonsäureestergruppen;
- (Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
- (Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen.
- (Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;
- (Db) nitro groups, optionally in combination with hydroxyl groups;
- (Dc) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
- (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
- (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
- (Df) polyoxy-C 2 - to C 4 -alkylene groups which are terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups;
- (Dg) carboxylic acid ester groups;
- (Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
- (Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings.
Der hydrophobe Kohlenwasserstoffrest in den obigen Detergens-Additiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, vorzugsweise von 113 bis 10.000, besonders bevorzugt von 300 bis 5.000, stärker bevorzugt von 300 bis 3.000, noch stärker bevorzugt von 500 bis 2.500 und insbesondere von 700 bis 2.500, vor allem von 800 bis 1500. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren Gruppierungen kommen insbesondere Polypropenyl-, Polybutenyl- und Polyisobutenylreste mit einem zahlenmittleren Molekulargewicht Mn von vorzugsweise jeweils 300 bis 5.000, besonders bevorzugt 300 bis 3.000, stärker bevorzugt 500 bis 2.500 noch stärker bevorzugt 700 bis 2.500 und insbesondere 800 bis 1.500 in Betracht.The hydrophobic hydrocarbon residue in the above detergent additives which provides the sufficient solubility in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500. As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groups are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n from preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1,500 into consideration.
Als Beispiele für obige Gruppen von Detergens-Additiven seien die folgenden genannt:
- Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000, besonders bevorzugt 500 bis 2500 und insbesondere 700 bis 2500. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, das bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der
EP-A 244 616 WO-A 94/24231
- Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene with M n = 300 to 5000, especially preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which are selected from the polyisobutene, which may contain up to 20% by weight of n-butene units, can be prepared by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are in particular from
EP-A 244 616 WO-A 94/24231
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in der
Nitrogruppen (Db), gegebenenfalls in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der
Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (Dc) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit Mn = 300 bis 5000 mit Ammoniak, Mono- oder Polyaminen, wie sie insbeson-dere in der
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (Dd) enthaltende Additive sind vorzugsweise Copolymere von C2- bis C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20.000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (De) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobernsteinsäurealkylesters, wie er insbesondere in der
Polyoxy-C2-C4-alkylengruppierungen (Df) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C60-Alkanolen, C6-bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkylcyclohexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Carbonsäureestergruppen (Dg) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 100 °C, wie sie insbesondere in der
Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder insbesondere Imidogruppen (Dh) enthaltende Additive sind vorzugsweise entsprechende Derivate von Alkyl- oder Alkenyl-substituiertem Bernsteinsäureanhydrid und insbesondere die entsprechenden Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = vorzugsweise 300 bis 5000, besonders bevorzugt 300 bis 3000, stärker bevorzugt 500 bis 2500, noch stärker bevorzugt 700 bis 2500 und insbesondere 800 bis 1500, mit Maleinsäureanhydrid auf thermischem Weg in einer En-Reaktion oder über das chlorierte Polyisobuten erhältlich sind. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureamide von Monoaminen, Säureamide von Di- oder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, oder Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Beim Vorliegen von Imidogruppierungen D(h) wird das weitere Detergens-Additiv im Sinne der vorliegenden Erfindung jedoch nur bis maximal 100 % der Gewichtsmenge an Verbindungen mit Betainstruktur eingesetzt. Derartige Kraftstoffadditive sind allgemein bekannt und beispielsweise in den Dokumenten (1) und (2) beschrieben. Bevorzugt handelt es sich um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen und besonders bevorzugt um die Umsetzungsprodukte von Polyisobutenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen. Von besonderem Interesse sind hierbei Umsetzungsprodukte mit aliphatischen Polyaminen (Polyalkylenimine) wie insbesondere Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin und Hexaethylenheptamin, welche eine Imidstruktur aufweisen.Derivatives derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by reaction of conventional or highly reactive polyisobutene having M n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene are available. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbonsäureimide with monoamines, Carbonsäureimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. In the presence of imido groups D (h), however, the further detergent additive according to the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure. Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (Di) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin oder Dimethylaminopropylamin. Die Polyisobutenyl-substituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der
Dem Kraftstoff können ein oder mehrere der genannten Detergens-Additive in solch einer Menge zugegeben werden, dass die Dosierrate an diesen Detergens-Additiven vozugsweise 25 bis 2500 Gew.-ppm, insbesondere 75 bis 1500 Gew.-ppm, vor allem 150 bis 1000 Gew.-ppm, beträgt.One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.
Mitverwendete Trägeröle können mineralischer oder synthetischer Natur sein. Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 bis 2000, aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500 °C, erhältlich aus unter Hochdruck katalytisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle.Co-used carrier oils may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
Beispiele für geeignete synthetische Trägeröle sind Polyolefine (Polyalphaolefine oder Polyinternalolefine), (Poly)ester, Poly)alkoxylate, Polyether, aliphatische Polyetheramine, alkylphenolgestartete Polyether, alkylphenolgestartete Polyetheramine und Carbonsäureester langkettiger Alkanole.Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of suitable polyolefins are olefin polymers having M n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).
Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2-bis C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkyl-cyclohexanolen oder C1- bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der
Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, wie sie insbesondere in der
Weitere geeignete Trägerölsysteme sind beispielsweise in der
Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, vorzugsweise etwa 5 bis 30, besonders bevorzugt 10 bis 30 und insbesondere 15 bis 30 C3- bis C6-Alkylenoxideinheiten, z. B. Propylenoxid-, n-Butylenoxid- und Isobutylenoxid-Einheiten oder Gemischen davon, pro Alkoholmolekül. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkyl-substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6- bis C18-Alkylrest steht. Als besondere Beispiele sind zu nennen Tridecanol und Nonylphenol. Besonders bevorzugte alkoholgestartete Polyether sind die Umsetzungsprodukte (Polyveretherungsprodukte) von einwertigen aliphatischen C6- bis C18-Alkoholen mit C3- bis C6-Alkylenoxiden. Beispiele für einwertige aliphatische C6-C18-Alkohole sind Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonylalkohol, Decanol, 3-Propylheptanol, Undecanol, Dodecanol, Tridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Octadecanol und deren Konstitutions- und Stellungsisomere. Die Alkohole können sowohl in Form der reinen Isomere als auch in Form technischer Gemische eingesetzt werden. Ein besonders bevorzugter Alkohol ist Tridecanol. Beispiele für C3- bis C6-Alkylenoxide sind Propylenoxid, wie 1,2-Propylenoxid, Butylenoxid, wie 1,2-Butylenoxid, 2,3-Butylenoxid, Isobutylenoxid oder Tetrahydrofuran, Pentylenoxid und Hexylenoxid. Besonders bevorzugt sind hierunter C3- bis C4-Alkylenoxide, d.h. Propylenoxid wie 1,2-Propylenoxid und Butylenoxid wie 1,2-Butylenoxid, 2,3-Butylenoxid und Isobutylenoxid. Speziell verwendet man Butylenoxid.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides. Examples of monohydric aliphatic C 6 -C 18 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, Butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particularly preferred are C 3 to C 4 alkylene oxides, ie, propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used.
Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der
Besondere Trägeröle sind synthetische Trägeröle, wobei die zuvor beschriebenen alkoholgestarteten Polyether besonders bevorzugt sind.Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
Das Trägeröl bzw. das Gemisch verschiedener Trägeröle wird dem Kraftstoff in einer Menge von vorzugsweise 1 bis 1000 Gew.-ppm, besonders bevorzugt von 10 bis 500 Gew.-ppm und insbesondere von 20 bis 100 Gew.-ppm zugesetzt.The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
Geeignete Kaltfließverbesserer sind im Prinzip alle organischen Verbindungen, welche in der Lage sind, das Fließverhalten von Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen in der Kälte zu verbessern. Zweckmäßigerweise müssen sie eine ausreichende Öllöslichkeit aufweisen. Insbesondere kommen hierfür die üblicherweise bei Mitteldestillaten aus fossilem Ursprung, also bei üblichen mineralischen Dieselkraftstoffen, eingesetzten Kaltfließverbesserer ("middle distillate flow improvers" , "MDFI" ) in Betracht. Jedoch können auch organische Verbindungen verwendet werden, die beim Einsatz in üblichen Dieselkraftstoffen zum Teil oder überwiegend die Eigenschaften eines Wax Anti-Settling Additivs ("WASA") aufweisen. Auch können sie zum Teil oder überwiegend als Nukleatoren wirken. Es können aber auch Mischungen aus als MDFI wirksamen und/oder als WASA wirksamen und/oder als Nukleatoren wirksamen organischen Verbindungen eingesetzt werden.Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.
Typischerweise wird der Kaltfließverbesserer ausgewählt aus:
- (K1) Copolymeren eines C2- bis C40-Olefins mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
- (K2) Kammpolymeren;
- (K3) Polyoxyalkylenen;
- (K4) polaren Stickstoffverbindungen;
- (K5) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
- (K6) Poly(meth)acrylsäureestern.
- (K1) copolymers of a C 2 to C 40 olefin with at least one further ethylenically unsaturated monomer;
- (K2) comb polymers;
- (K3) polyoxyalkylenes;
- (K4) polar nitrogen compounds;
- (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and
- (K6) poly (meth) acrylic acid esters.
Es können sowohl Mischungen verschiedener Vertreter aus einer der jeweiligen Klassen (K1) bis (K6) als auch Mischungen von Vertretern aus verschiedenen Klassen (K1) bis (K6) eingesetzt werden.Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.
Geeignete C2- bis C40-Olefin-Monomere für die Copolymeren der Klasse (K1) sind beispielsweise solche mit 2 bis 20, insbesondere 2 bis10 Kohlenstoffatomen sowie mit 1 bis 3, vorzugsweise mit 1 oder 2, insbesondere mit einer Kohlenstoff-Kohlenstoff-Doppelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (α -Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α -Olefine, besonders bevorzugt α -Olefine mit 2 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1-Buten, 1-Penten, 1-Hexen und vor allem Ethylen.Suitable C 2 to C 40 olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
Bei den Copolymeren der Klasse (K1) ist das wenigstens eine weitere ethylenisch ungesättigte Monomer vorzugsweise ausgewählt unter Carbonsäurealkenylestern, (Meth)Acrylsäureestern und weiteren Olefinen.In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
Werden weitere Olefine mit einpolymerisiert, sind dies vorzugsweise höhermolekulare als das oben genannte C2- bis C40-Olefin-Basismonomere. Setzt man beispielsweise als Olefin-Basismonomer Ethylen oder Propen ein, eignen sich als weitere Olefine insbesondere C10- bis C40-α -Olefine. Weitere Olefine werden in den meisten Fällen nur dann mit einpolymerisiert, wenn auch Monomere mit Carbonsäureester-Funktionen eingesetzt werden.If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 to C 40 olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C 10 - to C 40 -α-olefins are particularly suitable as further olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
Geeignete (Meth)Acrylsäureester sind beispielsweise Ester der (Meth)Acrylsäure mit C1- bis C20-Alkanolen, insbesondere C1- bis C10-Alkanolen, vor allem mit Methanol, Ethanol, Propanol, Isopropanol, n-Butanol, sec.-Butanol, Isobutanol, tert.-Butanol, Pentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol und Decanol sowie Strukturisomeren hiervon.Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
Geeignete Carbonsäurealkenylester sind beispielsweise C2- bis C14-Alkenylester, z.B. die Vinyl- und Propenylester, von Carbonsäuren mit 2 bis 21 Kohlenstoffatomen, deren Kohlenwasserstoffrest linear oder verzweigt sein kann. Bevorzugt sind hierunter die Vinylester. Unter den Carbonsäuren mit verzweigtem Kohlenwasserstoffrest sind solche bevorzugt, deren Verzweigung sich in der α-Position zur Carboxylgruppe befindet, wobei das α-Kohlenstoffatom besonders bevorzugt tertiär ist, d. h. die Carbonsäure eine sogenannte Neocarbonsäure ist. Vorzugsweise ist der Kohlenwasserstoffrest der Carbonsäure jedoch linear.Suitable carboxylic alkenyl esters are, for example, C 2 -C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical are those preferably, whose branching is in the α-position to the carboxyl group, wherein the α-carbon atom is particularly preferably tertiary, ie, the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.
Beispiele für geeignete Carbonsäurealkenylester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Neopentansäurevinylester, Hexansäurevinylester, Neononansäurevinylester, Neodecansäurevinylester und die entsprechenden Propenyl-ester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Carbonsäurealkenylester ist Vinylacetat; typische hieraus resultierende Copolymere der Gruppe (K1) sind die mit am häufigsten eingesetzten Ethylen-Vinylacetat-Copolymere ("EVA").
Besonders vorteilhaft einsetzbare Ethylen-Vinylacetat-Copolymere und ihre Herstellung sind in der
Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are in the
Als Copolymere der Klasse (K1) sind auch solche geeignet, die zwei oder mehrere voneinander verschiedene Carbonsäurealkenylester einpolymerisiert enthalten, wobei diese sich in der Alkenylfunktion und/oder in der Carbonsäuregruppe unterscheiden. Ebenfalls geeignet sind Copolymere, die neben dem/den Carbonsäurealkenylester(n) wenigstens ein Olefin und/oder wenigstens ein (Meth)Acrylsäureester einpolymerisiert enthalten.Also suitable as copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
Auch Terpolymere aus einem C2- bis C40-α -Olefin, einem C1- bis C20-Alkylester einer ethylenisch ungesättigten Monocarbonsäure mit 3 bis 15 Kohlenstoffatomen und einem C2- bis C14-Alkenylester einer gesättigten Monocarbonsäure mit 2 bis 21 Kohlenstoffatomen sind als Copolymere der Klasse (K1) geeignet. Derartige Terpolymere sind in der
Das wenigstens eine oder die weiteren ethylenisch ungesättigten Monomeren sind in den Copolymeren der Klasse (K1) in einer Menge von vorzugsweise 1 bis 50 Gew.-%, insbesondere von 10 bis 45 Gew.-% und vor allem von 20 bis 40 Gew.-%, bezogen auf das Gesamtcopolymer, einpolymerisiert. Der gewichtsmäßige Hauptanteil der Monomereinheiten in den Copolymeren der Klasse (K1) stammt somit in der Regel aus den C2- bis C40-Basis-Olefinen.The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) is thus usually derived from the C 2 to C 40 based olefins.
Die Copolymere der Klasse (K1) weisen vorzugsweise ein zahlenmittleres Molekulargewicht Mn von 1000 bis 20.000, besonders bevorzugt von 1000 bis 10.000 und insbesondere von 1000 bis 8000 auf.The copolymers of class (K1) preferably have a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
Typische Kammpolymere der Komponente (K2) sind beispielsweise durch die Copolymerisation von Maleinsäureanhydrid oder Fumarsäure mit einem anderen ethylenisch ungesättigten Monomer, beispielsweise mit einem α -Olefin oder einem ungesättigten Ester wie Vinylacetat, und anschließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere geeignete Kammpolymere sind Copolymere von α -Olefinen und veresterten Comonomeren, beispielsweise veresterte Copolymere von Styrol und Maleinsäureanhydrid oder veresterte Copolymere von Styrol und Fumarsäure. Geeignete Kammpolymere können auch Polyfumarate oder Polymaleinate sein. Außerdem sind Homo- und Copolymere von Vinylethern geeignete Kammpolymere. Als Komponente der Klasse (K2) geeignete Kammpolymere sind beispielsweise auch solche, die in der
Als Komponente der Klasse (K3) geeignete Polyoxyalkylene sind beispielsweise Polyoxyalkylenester, Polyoxyalkylenether, gemischte Polyoxyalkylenesterether und Gemische davon. Bevorzugt enthalten diese Polyoxyalkylenverbindungen wenigstens eine, vorzugsweise wenigstens zwei lineare Alkylgruppen mit jeweils 10 bis 30 Kohlenstoffatomen und eine Polyoxyalkylengruppe mit einem zahlenmittleren Molekulargewicht von bis zu 5000. Derartige Polyoxyalkylenverbindungen sind beispielsweise in der
Als Komponente der Klasse (K4) geeignete polare Stickstoffverbindungen können sowohl ionischer als auch nicht ionischer Natur sein und besitzen vorzugsweise wenigstens einen, insbesondere wenigstens zwei Substituenten in Form eines tertiären Stickstoffatoms der allgemeinen Formel >NR7, worin R7 für einen C8- bis C40-Kohlenwasserstoffrest steht. Die Stickstoffsubstituenten können auch quaternisiert, das heißt in kationischer Form, vorliegen. Beispiele für solche Stickstoffverbindungen sind Ammoniumsalze und/oder Amide, die durch die Umsetzung wenigstens eines mit wenigstens einem Kohlenwasserstoffrest substituierten Amins mit einer Carbonsäure mit 1 bis 4 Carboxylgruppen bzw. mit einem geeignetem Derivat davon erhältlich sind. Vorzugsweise enthalten die Amine wenigstens einen linearen C8- bis C40-Alkylrest. Zur Herstellung der genannten polaren Stickstoffverbindungen geeignete primäre Amine sind beispielsweise Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tetradecylamin und die höheren linearen Homologen, hierzu geeignete sekundäre Amine sind beispielsweise Dioctadecylamin und Methylbehenylamin. Geeignet sind hierzu auch Amingemische, insbesondere großtechnisch zugängliche Amingemische wie Fettamine oder hydrierte Tallamine, wie sie beispielsweise in
Insbesondere ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbon-säuren) mit primären oder sekundären Aminen. Die diesem Umsetzungsprodukt zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) enthalten vorzugsweise mindestens 3 Carboxylgruppen, insbesondere 3 bis 12, vor allem 3 bis 5 Carboxylgruppen. Die Carbonsäure-Einheiten in den Polycarbonsäuren weisen vorzugsweise 2 bis 10 Kohlenstoffatome auf, insbesondere sind es Essigsäure-Einheiten. Die Carbonsäure-Einheiten sind in geeigneter Weise zu den Polycarbonsäuren verknüpft, meist über ein oder mehrere Kohlenstoff- und/oder Stickstoffatome. Vorzugsweise sind sie an tertiäre Stickstoffatome angebunden, die im Falle mehrerer Stickstoffatome über Kohlenwasserstoffketten verbunden sind.In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines. The poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
Vorzugsweise ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt auf Basis von mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) der allgemeinen Formel IIa oder IIb
Weiterhin ist das bevorzugte öllösliche Umsetzungsprodukt der Komponente (K4), insbesondere das der allgemeinen Formel IIa oder IIb, ein Amid, ein Amidammoniumsalz oder ein Ammoniumsalz, in dem keine, eine oder mehrere Carbonsäuregruppen in Amidgruppen übergeführt sind.Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
Geradkettige oder verzweigte C2- bis C6-Alkylengruppen der Variablen A sind beispielsweise 1,1-Ethylen, 1,2-Propylen, 1,3-Propylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2-Methyl-1,3-propylen, 1,5-Pentylen, 2-Methyl-1,4-butylen, 2,2-Dimethyl-1,3-propylen, 1,6-Hexylen (Hexamethylen) und insbesondere 1,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome.Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
C1- bis C19-Alkylengruppen der Variablen B sind vor beispielsweise 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbesondere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome.C 1 - to C 19 -alkylene groups of the variables B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene , Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (K4) sind üblicherweise Monoamine, insbesondere aliphatische Monoamine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen.The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
Meist sind diese den öllöslichen Umsetzungsprodukten der Komponente (K4) zugrundeliegenden Amine sekundären Amine und weisen die allgemeine Formel HN(R8)2 auf, in der die beiden Variablen R8 unabhängig voneinander jeweils geradkettige oder verzweigte C10- bis C30-Alkylreste, insbesondere C14- bis C24-Alkylreste bedeuten. Diese längerkettigen Alkylreste sind vorzugsweise geradkettig oder nur in geringem Grade verzweigt. In der Regel leiten sich die genannten sekundären Amine hinsichtlich ihrer längerkettigen Alkylreste von natürlich vorkommenden Fettsäure bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R8 gleich.In most cases, these amines are secondary amines on which the oil-soluble reaction products of component (K4) are based and have the general formula HN (R 8 ) 2 in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives. Preferably, the two radicals R 8 are the same.
Die genannten sekundären Amine können mittels Amidstrukturen oder in Form der Ammoniumsalze an die Polycarbonsäuren gebunden sein, auch kann nur ein Teil als Amidstrukturen und ein anderer Teil als Ammoniumsalze vorliegen. Vorzugsweise liegen nur wenige oder keine freien Säuregruppen vor. Vorzugsweise liegen die öllöslichen Umsetzungsprodukte der Komponente (K4) vollständig in Form der Amidstrukturen vor.The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.
Typische Beispiele für derartige Komponenten (K4) sind Umsetzungsprodukte der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure mit jeweils 0,5 bis 1,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1,2 Mol pro Carboxylgruppe, Dioleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditalgfettamin. Eine besonders bevorzugte Komponente (K4) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditalgfettamin.Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine , Dipalmitinamin, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
Als weitere typische Beispiele für die Komponente (K4) seien die N,N-Dialkylammoniumsalze von 2-N' ,N' -Dialkylamidobenzoaten, beispielsweise das Reaktionsprodukt aus 1 Mol Phthalsäureanhydrid und 2 Mol Ditalgfettamin, wobei letzteres hydriert oder nicht hydriert sein kann, und das Reaktionsprodukt von 1 Mol eines Alkenylspirobislactons mit 2 Mol eines Dialkylamins, beispielsweise Ditalgfettamin und/oder Talgfettamin, wobei die beiden letzteren hydriert oder nicht hydriert sein können, genannt.Further typical examples of the component (K4) include the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter may be hydrogenated or unhydrogenated, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or not hydrogenated, called.
Weitere typische Strukturtypen für die Komponente der Klasse (K4) sind cyclische Verbindungen mit tertiären Aminogruppen oder Kondensate langkettiger primärer oder sekundärer Amine mit carbonsäurehaltigen Polymeren, wie sie in der
Als Kaltfließverbesserer der Komponente der Klasse (K5) geeignete Sulfocarbonsäuren, Sulfonsäuren oder deren Derivate sind beispielsweise die öllöslichen Carbonsäureamide und Carbonsäureester von ortho-Sulfobenzoesäure, in denen die Sulfonsäurefunktion als Sulfonat mit alkylsubstituierten Ammoniumkationen vorliegt, wie sie in der
Als Kaltfließverbesserer der Komponente der Klasse (K6) geeignete Poly(meth)acrylsäureester sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäureestern. Bevorzugt sind Copolymere von wenigstens zwei voneinander verschiedenen (Meth)Acrylsäureestern, die sich bezüglich des einkondensierten Alkohols unterscheiden. Gegebenenfalls enthält das Copolymer noch ein weiteres, davon verschiedenes olefinisch ungesättigtes Monomer einpolymerisiert. Das gewichtsmittlere Molekulargewicht des Polymers beträgt vorzugsweise 50.000 bis 500.000. Ein besonders bevorzugtes Polymer ist ein Copolymer von Methacrylsäure und Methacrylsäureestern von gesättigten C14- und C15-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der
Dem Mitteldestillat-Kraftstoff bzw. Dieselkraftstoff wird der Kaltfließverbesserer bzw. das Gemisch verschiedener Kaltfließverbesserer in einer Gesamtmenge von vorzugsweise 10 bis 5000 Gew.-ppm, besonders bevorzugt von 20 bis 2000 Gew.-ppm, stärker bevorzugt von 50 bis 1000 Gew.-ppm und insbesondere von 100 bis 700 Gew.-ppm, z.B. von 200 bis 500 Gew.-ppm, zugegeben.The middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.
Geeignete Schmierfähigkeitsverbesserer (Lubricity Improver bzw. Friction Modifier) basieren üblicherweise auf Fettsäuren oder Fettsäureestern. Typische Beispiele sind Tallölfettsäure, wie beispielsweise in der
Geeignete Korrosionsinhibitoren sind z.B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z.B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethanolamine und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland) oder HiTEC 536 (Ethyl Corporation) vertrieben werden.Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
Geeignete Demulgatoren sind z.B. die Alkali- oder Erdalkalisalze von Alkyl-substituierten Phenol- und Naphthalinsulfonaten und die Alkali- oder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen wie Alkoholalkoxylate, z.B. Alkoholethoxylate, Phenolalkoxylate, z.B. tert-Butylphenolethoxylat oder tert-Pentylphenolethoxylat, Fettsäuren, Alkylphenole, Kondensationsprodunkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopolymeren, Polyethylenimine oder auch Polysiloxane.Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
Geeignete Dehazer sind z.B. alkoxylierte Phenol-Formaldehyd-Kondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Petrolite).Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.
Geeignete Antischaummittel sind z.B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) und RHODOSIL (Rhone Poulenc).Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
Geeignete Cetanzahlverbesserer sind z.B. aliphatische Nitrate wie 2-Ethylhexylnitrat und Cyclohexylnitrat sowie Peroxide wie Di-tert-butylperoxid.Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
Geeignete Antioxidantien sind z.B. substituierte Phenole, wie 2,6-Di-tert.-butylphenol und 6-Di-tert.-butyl-3-methylphenol sowie Phenylendiamine wie N,N'-Di-sec.-butyl-p-phenylendiamin.Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
Geeignete Metalldeaktivatoren sind z.B. Salicylsäurederivate wie N,N'-Disalicyliden-1,2-propandiamin.Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
Geeignete sind z.B. unpolare organische Lösungsmittel wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, Xylole, "white spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben werden, sowie polare organische Lösungsmittel, beispielsweise Alkohole wie 2-Ethylhexanol, Decanol und Isotridecanol. Derartige Lösungsmittel gelangen meist zusammen mit den vorgenannten Additiven und Co-Additiven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Dieselkraftstoff.Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2 Ethylhexanol, decanol and isotridecanol. Such solvents usually enter the diesel fuel together with the abovementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.
Das erfindungsgemäße Additiv eignet sich in hervorragender Weise als Kraftstoffzusatz und kann im Prinzip in jeglichen Kraftstoffen eingesetzt werden. Es bewirkt eine ganze Reihe von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren mit Kraftstoffen. Bevorzugt wird das erfindungsgemäße quaternisierte Additiv in Mitteldestillat-Kraftstoffen, insbesondere Dieselkraftstoffen, eingesetzt.The additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of internal combustion engines with fuels. The quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
Gegenstand der vorliegenden Erfindung sind daher auch Kraftstoffe, insbesondere Mitteldestillat-Kraftstoffe, mit einem als Zusatzstoff zur Erzielung von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren, beispielsweise von Dieselmotoren, insbesondere von direkteinspritzenden Dieselmotoren, vor allem von Dieselmotoren mit Common-Rail-Einspritzsystemen, wirksamen Gehalt an dem erfindungsgemäßen quaternisierten Additiv. Dieser wirksame Gehalt (Dosierrate) liegt in der Regel bei 10 bis 5000 Gew.-ppm, vorzugsweise bei 20 bis 1500 Gew.-ppm, insbesondere bei 25 bis 1000 Gew.-ppm, vor allem bei 30 bis 750 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Kraftstoff.The present invention therefore also fuels, especially middle distillate fuels, with an effective as an additive to achieve beneficial effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially of diesel engines with common rail injection systems, effective content on the quaternized additive according to the invention. This effective content (dosage rate) is usually 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel.
Bei Mitteldestillat-Kraftstoffen wie Dieselkraftstoffen oder Heizölen handelt es sich vorzugsweise um Erdölraffinate, die üblicherweise einen Siedebereich von 100 bis 400°C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360°C oder auch darüber hinaus. Dies können aber auch so genannte "Ultra Low Sulfur Diesel" oder "City Diesel" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 345°C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285°C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen mineralischen Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen sind auch solche, die durch Kohlevergasung oder Gasverflüssigung ["gas to liquid" (GTL)-Kraftstoffe] oder durch Biomasse-Verflüssigung ["biomass to liquid" (BTL)-Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Mitteldestillat-Kraftstoffe bzw. Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Biodiesel oder Bioethanol.Middle distillate fuels, such as diesel fuels or fuel oils, are preferably petroleum raffinates, which usually have a boiling range of from 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the mineral middle distillate mineral fuels or diesel fuels available through refining, those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
Die Qualitäten der Heizöle und Dieselkraftstoffe sind beispielsweise in DIN 51603 und EN 590 näher festgelegt (vgl. auch
Das erfindungsgemäße quaternisierte Additiv kann neben seiner Verwendung in den oben genannten Mitteldestillat-Kraftstoffen aus fossilem, pflanzlichem oder tierischem Ursprung, die im wesentlichen Kohlenwasserstoffmischungen darstellen, auch in Mischungen aus solchen Mitteldestillaten mit Biobrennstoffölen (Biodiesel) eingesetzt werden. Derartige Mischungen werden im Sinne der vorliegenden Erfindung auch von dem Begriff "Mitteldestillat-Kraftstoff" umfasst. Sie sind handelsüblich und enthalten meist die Biobrennstofföle in untergeordneten Mengen, typischerweise in Mengen von 1 bis 30 Gew.-% insbesondere von 3 bis 10 Gew.-%, bezogen auf die Gesamtmenge aus Mitteldestillat fossilen, pflanzlichem oder tierischen Ursprungs und Biobrennstofföl.In addition to its use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). For the purposes of the present invention, such mixtures are also encompassed by the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
Biobrennstofföle basieren in der Regel auf Fettsäureestern, vorzugsweise im wesentlichen auf Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere C1- bis C4-Alkylester, verstanden, die durch Umesterung der in pflanzlichen und/oder tierischen Ölen und/oder Fetten vorkommenden Glyceride, insbesondere Triglyceride, mittels Niedrigalkoholen, beispielsweise Ethanol oder vor allem Methanol ("FAME"), erhältlich sind. Typische Niedrigalkylester auf Basis von pflanzlichen und/oder tierischen Ölen und/oder Fetten, die als Biobrennstofföl oder Komponenten hierfür Verwendung finden, sind beispielsweise Sonnenblumenmethylester, Palmölmethylester ("PME"), Sojaölmethylester ("SME") und insbesondere Rapsölmethylester ("RME").Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, in particular C 1 - to C 4 alkyl esters, understood by transesterification in plant and / or animal oils and / or fats occurring glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol ("FAME"), are available. Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester ("RME"). ,
Besonders bevorzugt handelt es sich bei den Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen um solche mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel.The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.
Als Ottokraftstoffe kommen alle handelsüblichen Ottokraftstoffzusammensetzungen in Betracht. Als typischer Vertreter soll hier der marktübliche Eurosuper Grundkraftstoff gemäß EN 228 genannt werden. Weiterhin sind auch Ottokraftstoffzusammensetzungen der Spezifikation gemäß
Das erfindungsgemäße quaternisierte Additiv eignet sich insbesondere als Kraftstoffzusatz in Kraftstoffzusammensetzungen, insbesondere in Dieselkraftstoffen, zur Überwindung der eingangs geschilderten Probleme bei direkteinspritzenden Dieselmotoren, vor allem bei solchen mit Common-Rail-Einspritzsystemen.The quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.
Die Erfindung wird nun anhand der folgenden Ausführungsbeispiele näher beschrieben:The invention will now be described in more detail with reference to the following exemplary embodiments:
Das Vorliegen von Amid bzw. Imid in einer Probe wird IR-spektrometrisch überprüft. Die charakteristische IR-Bande für Amid liegt bei 1667 ± 5 cm-1, während die charakteristische IR-Bande des Imids bei 1705 ± 5 cm-1 liegt.The presence of amide or imide in a sample is checked by IR spectrometry. The characteristic IR band for amide is 1667 ± 5 cm -1 , while the characteristic IR band of the imide is 1705 ± 5 cm -1 .
Die Proben wurden dazu in Solvesso 50%-ig (m/m) verdünnt und in einer 29 µ m-CaF2-Küvette vermessen.The samples were diluted in Solvesso 50% (m / m) and measured in a 29 μ m CaF2 cuvette.
Die Durchführung erfolgt nach den Standardbestimmungen gemäß CEC F-23-1-01.The procedure is carried out according to the standard regulations according to CEC F-23-1-01.
Zur Untersuchung des Einflusses der Additive auf die Performance von direkteinspritzenden Dieselmotoren wurde der Leistungsverlust (powerloss) in Anlehnung an die offizielle Testmethode CEC F-098-08 bestimmt. Der Leistungsverlust ist ein direktes Maß für Bildung von Ablagerungen in den Injektoren.To investigate the influence of the additives on the performance of direct injection diesel engines, the power loss was determined according to the official test method CEC F-098-08. The power loss is a direct measure of the formation of deposits in the injectors.
Verwendet wurde ein direkteinspritzender Dieselmotor mit Common-Rail-System gemäß Testmethoden CEC F-098-08. Als Kraftstoff wurde ein handelsüblicher Dieselkraftstoff der Fa. Haltermann (RF-06-03) eingesetzt. Diesem wurden zur künstlichen Anregung der Bildung von Ablagerungen an den Injektoren 1 Gew.-ppm Zink in Form einer Zink-Didodecanoatlösung zugesetzt. Die Ergebnisse veranschaulichen den relativen Leistungsverlust bei 4000 rpm gemessen während eines 12-stündigen Dauerbetriebs. Der Wert "t0" gibt dabei den Leistungsverlust normiert (100%) auf den Wert nach 10 Minuten an; der Wert "t1" gibt den Leistungsverlust normiert auf den Wert nach einer Stunde an.A direct injection diesel engine with common rail system was used according to test methods CEC F-098-08. The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To this was added 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors. The results illustrate the relative power loss measured at 4000 rpm during a 12-hour continuous operation. The value "t0" indicates the power loss normalized (100%) to the value after 10 minutes; the value "t1" indicates the power loss normalized to the value after one hour.
Bei der Lagerung von Dieselkraftstoffen im Lager- bzw. Fahrzeugtank bei Temperaturen unterhalb des Cloud Points (CP) können sich ausgefallene Paraffine absetzen. Die sich dabei bildende paraffinreiche Bodenphase hat ein schlechteres Kälteverhalten, kann Filter von Fahrzeugen verstopfen und so zum Zusammenbruch der Fördermenge führen.The storage of diesel fuel in the storage or vehicle tank at temperatures below the cloud point (CP) can precipitate paraffins. The resulting paraffin-rich soil phase has a worse cold behavior, can clog filters of vehicles and thus lead to the collapse of the flow rate.
Mit dem KS - Test wird eine mögliche Sedimentation in Fahrzeugtanks simuliert und visuell ausgewertet. Von der im Test erhaltenen, mit Paraffinen angereicherten Dieselkraftstoffphase wird der CP und CFPP-Wert ermittelt. Der Vergleich dieser Werte mit denen des unsedimentierten Kraftstoffes gestattet Rückschlüsse auf das Kälteverhalten des Kraftstoffes. Dazu werden Delta CP oder Delta CFPP Werte bestimmt.With the KS - test a possible sedimentation in vehicle tanks is simulated and visually evaluated. From the paraffin-enriched diesel fuel phase obtained in the test the CP and CFPP value is determined. The comparison of these values with those of the unsedimented fuel allows conclusions to be drawn about the low-temperature behavior of the fuel. Delta CP or Delta CFPP values are determined for this purpose.
Bei dem Test wird der zu prüfende, gegebenenfalls additivierte Dieselkraftstoff (DK) für insgesamt 16 h bei - 13°C aufbereitet. Es erfolgt eine visuelle Beurteilung. Anschließend werden 80 Vol%-Oberphase des Kraftstoffs von oben her vorsichtig abgesaugt. Nach Erwärmen und Homogenisieren der verbliebenen 20%-Unterphase werden davon der Cloudpoint (CPKS) und der Cold Filter Plugging Point (CFPPKS) mit an sich bekannten Apparaturen bestimmt.During the test, the diesel fuel (DK) to be tested, if necessary, is treated for a total of 16 hours at - 13 ° C. There is a visual assessment. Subsequently, 80% by volume of the upper phase of the fuel are carefully removed by suction from above. After heating and homogenizing the remaining 20% subphase, the cloud point (CPKS) and the cold filter plugging point (CFPPKS) are determined therefrom by means of apparatus known per se.
Zur Durchführung werden die benötigten Probenmengen zur Abtrennung von Schmutz, Kokerbestandteilen, Wasser oder sonstigen ungelösten Verunreinigungen über ein Faltenfilter (nach DIN EN 116) abfiltriert. Das Probengefäß (skalierter Messzylinder) wird mit 550 ml Probenflüssigkeit befüllt. Die Probe wird, sofern erforderlich, mit Additiv versetzt. In einem Wasserbad erfolgt eine Erwärmung auf 50°C. Das Probengefäß wird aus dem Wasserbad genommen und abgetrocknet. Durch Stürzen und Schütteln wird die Probe homogenisiert. Von Teilmengen werden die Ausgangswerte CP und CFPP ("Original") bestimmt. Durch Stehen an der Luft wird die Probentemperatur 25°C angenähert.To carry out the required amounts of sample for the separation of dirt, coker components, water or other undissolved impurities via a pleated filter (according to DIN EN 116) is filtered off. The sample vessel (scaled measuring cylinder) is filled with 550 ml sample liquid. The sample is mixed with additive if necessary. In a water bath is heated to 50 ° C. The sample vessel is removed from the water bath and dried. By dropping and shaking the sample is homogenized. Subsets are used to determine the initial values CP and CFPP ("Original"). By standing in air, the sample temperature is approximated to 25 ° C.
Das Probengefäß mit 500 ml Probeninhalt wird mittels Haltevorrichtung in ein Flüssigkeitsbad eingehängt. Temperierung beginnt bei 25°C. Die Probe wird innerhalb 2 h 40 min auf -13°C abgekühlt. Bei -13 °C wird die Probe 13 h 20 min gelagert.The sample vessel with 500 ml sample contents is suspended by means of holding device in a liquid bath. Temperature control starts at 25 ° C. The sample is cooled to -13 ° C within 2 h 40 min. At -13 ° C, the sample is stored for 13 h 20 min.
Mittels einer Absaugvorrichtung wird die Probe bis auf eine Restmenge von 100 ml (20 %) von oben her abgesaugt. Probenbewegungen und Turbulenzen sind so gering wie möglich zu halten. Das Probengefäß wird mit der darin verbliebenen 20% Unterphase auf 50°C erwärmt. Die Unterphase wird homogenisiert und zur Bestimmung der Endwerte von CP und CFPP (d.h. CPKS und CFPPKS) verwendet.By means of a suction device, the sample is aspirated to a residual amount of 100 ml (20%) from above. Sample movements and turbulence should be kept as low as possible. The sample vessel is heated to 50 ° C with the 20% lower phase remaining therein. The lower phase is homogenized and used to determine the final values of CP and CFPP (i.e., CPKS and CFPPKS).
Der Nachweis der Betain-Struktur in erfindungsgemäßen Additiven und deren Synthesevorstufen erfolgt durch Massenbestimmung unter Anwendung der Matrix Assisted Laser Desorption/Ionisation-Time Of Flight Mass Spectrometry (MALDI-TOF-MS). Die Analyse erfolgt unter folgenden Bedingungen:
- Verwendet wird das Gerät BIFLEX 3 der Fa. Bruker und ein UV-Laser der Wellenlänge 337nm. Die Laserleistung wird solange erhöht, bis die Austrittsschwelle der Ionen erreicht ist. Die Matrix besteht aus 20 g/l Dithranol in THF (ionengetauscht), wobei eine Polymerkonzentration von ca. 2 g/l in THF verwendet wird. Die Vorgehensweise ist folgende: die Matrix wird mit dem jeweiligen Polymer im Verhältnis 1:1 gemischt und 1 µl davon auf dem Target getrocknet ("dried-droplet technique"). Die getrockneten Fraktionen werden dann in 20 µl der Matrix-Lösung gelöst und schließend vermessen. Insgesamt werden pro
Messung 100 Einzelspektren addiert.
- The device BIFLEX 3 from Bruker and a UV laser with a wavelength of 337nm are used. The laser power is increased until the exit threshold of the ions is reached. The matrix consists of 20 g / l dithranol in THF (ion-exchanged), using a polymer concentration of about 2 g / l in THF. The procedure is as follows: the matrix is mixed with the respective polymer in a ratio of 1: 1 and 1 μl thereof dried on the target ("dried-droplet technique"). The dried fractions are then dissolved in 20 μl of the matrix solution and then measured. In total, 100 individual spectra are added per measurement.
Außerdem wird auch die Analyse über ESI-LC/MS (Electrospray Ionisation Liquid Chromatographie Mass Spectrometry) im Lösungsmittel THF durchgeführt. Dafür wird das LTQ/FT (Thermo) MS-System und das LC-System bestehend aus HP 1100 Bin Pumpe, HP 1100 ALS und HP 1100 DAD verwendet. Es werden ca. 10 mg Prüfsubstanz in 1 ml THF gelöst und bei Raumtemperatur vermessen. Die Auflösung beträgt 100.000.In addition, the analysis using ESI-LC / MS (Electrospray Ionization Liquid Chromatography Mass Spectrometry) is performed in the solvent THF. The LTQ / FT (Thermo) MS system and LC system consisting of HP 1100 Bin Pump, HP 1100 ALS and HP 1100 DAD are used for this. About 10 mg of test substance are dissolved in 1 ml of THF and measured at room temperature. The resolution is 100,000.
Die Bestimmung erfolgte nach den Vorschriften in dem von der Deutschen Wissenschaftlichen Gesellschaft für Erdöl, Erdgas und Kohle e.V. (DGMK) aufgestellten Kriterienkatalog zur Testung von Lubricity Additiven in Dieselkraftstoffen (DGMK-Report 531)The determination was carried out according to the regulations in the catalog of criteria for the testing of lubricity additives in diesel fuels, prepared by the German Scientific Society for Petroleum, Natural Gas and Coal (DGMK) (DGMK Report 531).
Im Kraftstoffsystem von Dieselfahrzeugen besteht die Möglichkeit, dass geringe Mengen an Motorenöl in den Dieselkraftstoffkreislauf gelangen. In einigen Fällen ist beobachtet worden, dass Reaktionen zwischen Motorenölbestandteilen und den in Dieselkraftstoffen enthaltenen Additiven auftraten, die zu Verstopfungen von Kraftstofffiltern und damit zum Ausfall von Fahrzeugen rührten. Deshalb wurde eine Prüfmethode entwickelt, mit deren Hilfe Reaktionen zwischen Motorenöl- und Dieselkraftstoffadditiven, die zu Filterverstopfungen führen würden, erkannt und beurteilt werden.In the fuel system of diesel vehicles, there is a possibility that small amounts of engine oil get into the diesel fuel cycle. In some cases it has been observed that reactions occurred between engine oil components and the additives contained in diesel fuels, which led to blockages of fuel filters and thus to the failure of vehicles. Therefore, a test method was developed to identify and assess reactions between engine oil and diesel fuel additives that would lead to filter blockages.
Das zu prüfende Additiv wird mit der gleichen Menge des festgelegten Motorenöls vermischt und über drei Tage bei 90 °C konditioniert. Nach dieser Konditionierung wird das Gemisch mit Dieselkraftstoff aufgefüllt, vermischt und mit Hilfe des SEDAB - Tests (DGMK Report 531, Anhang II-A) beurteilt. Die Ergebnisse aus beiden Prüfungen gestatten eine Aussage über die "Motorenölverträglichkeit" des zu prüfenden Dieselkraftstoffadditivs.The additive to be tested is mixed with the same amount of the specified motor oil and conditioned at 90 ° C for three days. After this conditioning will be the mixture is filled up with diesel fuel, mixed and assessed by means of the SEDAB test (DGMK Report 531, Annex II-A). The results from both tests allow a statement about the "engine oil compatibility" of the diesel fuel additive to be tested.
Geräte und Prüfmittel:
- 500 ml Erlenmeyerkolben mit NS19 Glasschliffstopfen
- alpha-Methylnaphtalin
- Dieselkraftstoff, welcher den SEDAB-Test einwandfrei besteht
- Motorenöl (CEC Reference Lub RL-189, SAE 15W-40)
- 500 ml Erlenmeyer flask with NS19 ground glass stopper
- alpha-methylnaphthalene
- Diesel fuel that passes the SEDAB test properly
- Motor oil (CEC Reference Lub RL-189, SAE 15W-40)
Der zur Durchführung des Tests vorgesehene DK sowie das Motorenöl sind vor ihrem ersten Einsatz mit Hilfe des SEDAB-Tests zu beurteilen. Hierzu werden 10 g Motorenöl in 500 ml DK gelöst. Eventuell sind zur Verbesserung der Löslichkeit 10 ml alpha-Methylnaphtalin zuzusetzen und die Homogenisierung zu wiederholen. Diese Mischung wird sofort im SEDAB-Test beurteilt. Ist die Mischung einwandfrei filtrierbar, so kann der DK für die Durchführung der Prüfung verwendet werden.The DK intended for the test and the engine oil shall be assessed before their first use by means of the SEDAB test. To do this, dissolve 10 g motor oil in 500 ml DC. It may be necessary to add 10 ml of alpha-methylnaphthalene to improve the solubility and to repeat the homogenization. This mixture is assessed immediately in the SEDAB test. If the mixture is perfectly filterable, the DK can be used to carry out the test.
In einen 500 ml Erlenmeyerkolben werden je 10 g Motorenöl und 10 g des zu überprüfenden Additivs eingewogen und anschließend durch Schwenken des Kolbens homogenisiert. Bei schlechter Mischbarkeit werden zusätzlich 10 ml alpha-Methylnaphtalin zugesetzt und erneut homogenisiert. Diese Mischung wird mit einem Glasstopfen verschlossen und drei Tage bei einer Temperatur von 90 °C im Trockenschrank konditioniert.10 g of engine oil and 10 g of the additive to be tested are weighed into a 500 ml Erlenmeyer flask and then homogenized by swirling the flask. In case of poor miscibility, an additional 10 ml of alpha-methylnaphthalene are added and homogenized again. This mixture is sealed with a glass stopper and conditioned for three days at a temperature of 90 ° C in a drying oven.
Nach der Konditionierung lässt man die Mischung eine Stunde bei Raumtemperatur abkühlen und beurteilt sie visuell auf eventuelle Ausscheidungen, Trübungen, Gelbildungen u.s.w. Die Mischung wird mit Dieselkraftstoff auf 500 ml aufgefüllt und gut durchmischt. Es erfolgt eine visuelle Beurteilung. Sollten sich Ausscheidungen gebildet haben, so sind diese vor der Durchführung des SEDAB- Tests durch kräftiges Schütteln zu suspendieren. Nach zwei Stunden Standzeit wird die Mischung erneut visuell beurteilt und dann über ein 0,8 µm Filter bei einer Druckdifferenz von 800 mbar (siehe SEDAB-Prüfvorschrift) filtriert, Die Gesamtmenge muss innerhalb der festgelegten Zeit filtrierbar sein.After conditioning, the mixture is allowed to cool for one hour at room temperature and visually assessed for any precipitation, turbidity, gelation, etc. The mixture is made up to 500 ml with diesel fuel and mixed thoroughly. There is a visual assessment. If precipitates have formed, they should be suspended by vigorous shaking before performing the SEDAB test. After two hours, the mixture is again visually assessed and then filtered through a 0.8 micron filter at a pressure difference of 800 mbar (see SEDAB test specification). The total amount must be filterable within the specified time.
Beim Auftreten von Ausscheidungen, Trübungen, Gelbildungen und/oder schlechter Filtrierbarkeit im SEDAB- Test ist das Additiv als nicht motorenölverträglich einzustufen. Bei guter Filtrierbarkeit und einwandfreiem visuellen Befund ist das Additiv als motorenölverträglich einzustufen.If exudates, turbidities, gel formations and / or poor filterability occur in the SEDAB test, the additive must be classified as non-engine oil compatible. With good filterability and perfect visual findings, the additive is classified as engine oil compatible.
500 ml eines vorbehandelten DKs werden dazu über ein Membranfilter gesaugt. Die Zeit in Sekunden, die gebraucht werden, um dieses Volumen bei 20±2 °C und 200 hPa (d.h. ca 800hPa Differenzdruck) zu filtrieren, wird bestimmt. Liegt diese über zwei Minuten, so wird die nach zwei Minuten erhaltene Filtratmenge notiert.500 ml of a pretreated DK are sucked through a membrane filter. The time in seconds needed to filter this volume at 20 ± 2 ° C and 200 hPa (i.e., about 800hPa differential pressure) is determined. If this is more than two minutes, the amount of filtrate obtained after two minutes is noted.
- Membranfilter: Fa. Sartorius aus Cellulosenitrat, weiß, glatt, 50 mm Durchmesser. Porenweite 0,8 µm.Membrane filter: Sartorius made of cellulose nitrate, white, smooth, 50 mm diameter. Pore size 0.8 μm.
- Filtrationsgerät: Filtrationseinrichtung mit 500 ml-Trichter: Sartorius SM 16 201Filtration device: Filtration device with 500 ml funnel: Sartorius SM 16 201
- Saugflasche: Fassungsvermögen 1000 mlSuction bottle: capacity 1000 ml
- Vakuumsystem: z.B. Vakuum-Constanter TOM-VAC 1 Automatic Zerosystem mit einem Mindestdruck von 200 hPa.Vacuum system: e.g. Vacuum Constant TOM-VAC 1 Automatic Zerosystem with a minimum pressure of 200 hPa.
- Trockenschrank zum Temperieren bei 90±3 °C ohne UmluftDrying cabinet for tempering at 90 ± 3 ° C without circulating air
- Pinzettetweezers
- Petrischale aus Glas, ca. 125 mm Durchmesser mitannehmbarem DeckelGlass Petri dish, about 125 mm in diameter with an acceptable lid
- Probengefäß: Standzylinder (Fassungsvermögen 500 ml) mit Glasschliff und Stopfen.Sample vessel: Stand cylinder (capacity 500 ml) with ground glass and stopper.
Zur Probenvorbereitung wird das Probengefäß der ursprünglichen Kraftstoffprobe mit 20 senkrechten Hüben geschüttelt. Man lässt die Probe 16 Stunden bei Raumtemperatur stehen. Unmittelbar vor der Messung wird der Kraftstoff nochmals durch Schütteln (10 Hübe) homogenisiert und in den 500-ml-Trichter der Prüfapparatur gegeben.For sample preparation, shake the sample vessel of the original fuel sample with 20 vertical strokes. The sample is allowed to stand for 16 hours at room temperature. Immediately before the measurement, the fuel is homogenized again by shaking (10 strokes) and placed in the 500 ml funnel of the test apparatus.
Die Membranfilter werden bei 90 ± 3 °C für eine halbe Stunde im Trockenschrank konditioniert und anschließend bis zu Verwendung in einem Exsikkator aufbewahrt. Der entsprechend vorbereitete Membranfilter wird in die Filtrationsapparatur eingelegt. Der 500 ml-Trichter wird mit der gesamten Probe (500 ml) befüllt und dann sofort ein Druck von 200 hPa (absolut, entspricht ca. 800 hPa Differenzdruck) angelegt. Es ist darauf zu achten, dass die Kraftstoffprobe nicht nachgegossen wird. Die Filtrationszeit wird auf volle Sekunden gerundet angegeben. Wird eine Filtrationszeit von zwei Minuten überschritten, ohne dass die gesamte Probe filtriert werden konnte, so wird die Prüfung beendet und das bis dahin durchgelaufene Volumen des Kraftstoffs gemessen. Die Angabe des Ergebnisses erfolgt in diesem Fall als "> 2 Minuten" und der bis zum Abbruch filtrierten Probenmenge (ml). Liegt die Filtrationszeit der Probe über zwei Minuten, sollte ein entsprechendes Muster für 30 Minuten auf 50 °C erwärmt und anschließend filtriert werden. Sofern das Messergebnis wiederum über zwei Minuten liegt, sollte die Gesamtverschmutzung des Kraftstoffs nach DIN 51 419 bestimmt werden. Nach der Filtration werden Trichter und Filter mit n-Heptan und nachfolgend mit Testbenzin (40/80) DK-frei gespült. Das Membranfilter wird mit einer Pinzette vorsichtig von der Filterplatte entfernt, in eine saubere Petrischale gelegt und für 30 Minuten mit halbgeöffnetem Deckel in einem Trockenschrank bei 90 ± 3 °C getrocknet. Danach wird die Petrischale mindestens 15 Minuten zum Abkühlen in den Exsikkator gestellt.The membrane filters are conditioned at 90 ± 3 ° C for half an hour in the oven and then stored in a desiccator until needed. The appropriately prepared membrane filter is placed in the filtration apparatus. The 500 ml funnel is filled with the entire sample (500 ml) and then immediately applied a pressure of 200 hPa (absolute, corresponds to about 800 hPa differential pressure). It is on it to make sure that the fuel sample is not refilled. The filtration time is given rounded to full seconds. If a filtration time of two minutes is exceeded without the entire sample being able to be filtered, the test is terminated and the volume of fuel that has passed through until then is measured. In this case, the result is given as "> 2 minutes" and the sample volume filtered until discontinuation (ml). If the filtration time of the sample is more than two minutes, an appropriate pattern should be heated to 50 ° C for 30 minutes and then filtered. If the measurement result is again over two minutes, the total contamination of the fuel according to DIN 51 419 should be determined. After filtration, funnel and filter are flushed with n-heptane and subsequently with white spirit (40/80) DK-free. The membrane filter is carefully removed from the filter plate with tweezers, placed in a clean Petri dish and dried for 30 minutes with half-open lid in a drying oven at 90 ± 3 ° C. Thereafter, the Petri dish is placed in the desiccator for at least 15 minutes to cool.
Proben, die nach dem oben beschriebenen Verfahren innerhalb von zwei Minuten filtrierbar sind, werden bzgl. der vorliegenden Prüfmethode als "unkritisch" eingestuft. Dieselkraftstoffe, die innerhalb dieser Zeit nicht filtrierbar sind, sind als "kritisch" einzustufen und können bei Fahrzeugen und Tankstellen zu Filterverstopfungen führen. Bei Proben mit kritischem Verhalten sollte das Membranfilter optisch (mikroskopisch) bzw. mittels Infrarotspektroskopie auf die Ursache der Verstopfens untersucht werden.Samples which can be filtered within two minutes by the method described above are classified as "non-critical" with respect to the present test method. Diesel fuels that can not be filtered within this time are classified as "critical" and can lead to filter blockages in vehicles and petrol stations. For samples with critical behavior, the membrane filter should be examined visually (microscopically) or by infrared spectroscopy for the cause of the blockage.
386.8 g (0,35 Mol) Polyisobutenbernsteinsäureanhydrid (PIBSA 1000) werden in einem 2 Liter Vierhalskolben bei Raumtemperatur unter einem schwachen N2-Strom in 176 g Solvesso 150 gelöst. Nach der Zugabe von 29.9 g (0,29 Mol) 3-Dimethylamino-1-propylamin (DMAPA) steigt die Reaktionstemperatur auf 40 °C an. Die Lösung wird 10 Minuten lang bei 40 °C gerührt. Anschließend werden 34.2 g (0,29 Mol) (1,2-Epoxyethyl)-benzol zugegeben und es folgt eine weitere Reaktionszeit von 7 Stunden bei 70 °C unter N2. Die Lösung wird abschließend mit 274.9 g Solvesso 150 auf einen Wirkstoffgehalt von 50 % eingestellt.386.8 g (0.35 mol) of polyisobutene succinic anhydride (PIBSA 1000) are dissolved in 176 g of Solvesso 150 in a 2 liter four-necked flask at room temperature under a gentle N 2 flow. After the addition of 29.9 g (0.29 mol) of 3-dimethylamino-1-propylamine (DMAPA), the reaction temperature rises to 40.degree. The solution is stirred for 10 minutes at 40 ° C. Subsequently, 34.2 g (0.29 mol) of (1,2-epoxyethyl) benzene are added and followed by a further reaction time of 7 hours at 70 ° C under N 2 . The solution is finally adjusted with 274.9 g Solvesso 150 to an active ingredient content of 50%.
Durch IR-Analyse konnte die Bildung des erfindungsgemäßen Amid-Additionsproduktes (A) nachgewiesen werden.By IR analysis, the formation of the amide addition product (A) according to the invention could be detected.
Mittels ESI-LC/MS und MALDI-TOF-MS wurde die Betain-Struktur von (A) experimentell belegt.By means of ESI-LC / MS and MALDI-TOF-MS, the betaine structure of (A) was experimentally confirmed.
Die gesamte Versuchsdurchführung erfolgt unter schwachem N2-Strom. PIBSA 1000 (481,61 g) und Pilot 900 Öl (84,99g) werden bei 110°C in der Vorlage gerührt. Dann wird DMAPA (37,28g) binnen 42 Minuten bei 110-115°C zudosiert. Man beobachtet eine leicht exotherme Reaktion. Anschließend wird auf 150°C hochgeheizt und 3h bei 150°C gerührt um Reaktionswasser zu entfernen. Der Ansatz wird dann auf Raumtemperatur gekühlt und nacheinander mit MeOH (152g), Essigsäure (21,91g) und Styroloxid (43,84g) versetzt. der Ansatz wird dann 5h am Rückfluss (67-69°C) gerührt. Nach Stehen über Nacht bei 30-35°C wird der Ansatz destillativ eingeengt (1h/ 6mbar / 36°C Ölbad). Die Auswaage von 661,1g wird mit Pilot900 Öl (493,07g) auf einen Wirkstoffgehalt von 50% eingestellt.The entire experiment is carried out under a weak N 2 stream. PIBSA 1000 (481.61 g) and Pilot 900 oil (84.99 g) are stirred at 110 ° C in the template. Then DMAPA (37.28 g) is added within 42 minutes at 110-115 ° C. One observes a slightly exothermic reaction. The mixture is then heated to 150 ° C and stirred for 3 h at 150 ° C to remove water of reaction. The reaction is then cooled to room temperature and treated successively with MeOH (152g), acetic acid (21.91g) and styrene oxide (43.84g). The mixture is then stirred for 5 h at reflux (67-69 ° C). After standing overnight at 30-35 ° C, the mixture is concentrated by distillation (1h / 6mbar / 36 ° C oil bath). The weight of 661.1g is adjusted to 50% drug content with Pilot900 Oil (493.07g).
Durch IR-Analyse konnte die Bildung des Imids (B) nachgewiesen werden.By IR analysis, the formation of imide (B) could be detected.
Mittels ESI-LC/MS und MALDI-TOF-MS wurde das Fehlen einer Betain-Struktur in (B) experimentell belegt.By means of ESI-LC / MS and MALDI-TOF-MS, the absence of a betaine structure in (B) was experimentally demonstrated.
In den folgenden Anwendungsbeispielen werden die Additive entweder als Reinsubstanz (so wie in obigen Herstellungsbeispielen synthetisiert) oder in Form eines Additiv-Paketes eingesetzt. Folgenden Pakete wurden verwendet
Die Ergebnisse sind in folgender Tabelle zusammengefasst
Die Versuchsergebnisse sind in
Dabei zeigt sich, dass bei gleicher Dosierung (100 mg/kg Wirkstoff, dh. 200 ppm Herstellungsbeispiel 1) das erfindungsgemäße Amid-Additiv (Rauten) und das Imid-Vergleichsadditiv (Dreiecke) den für unadditivierten Kraftstoff (Quadrate) beobachteten Leistungsverlust deutlich verringern, wobei jedoch das erfindungsgemäße Additiv den verbleibenden Leistungsverlust im Bereich von etwa 0,5% über die gesamte Versuchsdauer stabilisiert, d.h. 99.5 % der ursprünglichen Motor-Maximalleistung bleiben erhalten. Mit dem entsprechenden Vergleichsadditiv bleibt jedoch nur noch eine Leistung von 98,5% der ursprünglichen Motor-Maximalleistung erhalten.It shows that at the same dosage (100 mg / kg of active ingredient, ie 200 ppm of preparation example 1), the amide additive according to the invention (diamonds) and the imide comparison additive (triangles) observed that for unadditized fuel (squares) Significantly reducing power loss, however, the additive of the invention stabilizes the remaining power loss in the range of about 0.5% over the entire duration of the test, ie, 99.5% of the original maximum engine power is maintained. With the corresponding comparison additive, however, only a power of 98.5% of the original maximum engine power remains.
Kommerziell erhältlicher Winter-DK wurde in der in folgender Tabelle angegebenen Weise mit Additiv gemäß Herstellngsbeispiel 1 (#3) und Additiv gemäß Herstellungsbeispiel 2 (#2), sowie mit dem Additivpaket M2450 (#5) bzw. M2452 (#4) additiviert und einem KS-Test unterzogen. Als Vergleich (#1) diente DK mit Kaltfliessverbessereradditiv ohne Amid und Imid.Commercially available winter DK was additized in the manner indicated in the following table with Additive according to Preparation Example 1 (# 3) and additive according to Preparation Example 2 (# 2), as well as with the additive package M2450 (# 5) or M2452 (# 4) and subjected to a KS test. As a comparison (# 1) DK was used with cold flow improver additive without amide and imide.
Als Testkraftstoff wurde Dieselkraftstoff der Firma Bayernoil, (CP - 6,5°C) verwendet.As a test fuel diesel fuel from Bayernoil, (CP - 6.5 ° C) was used.
Sämtliche Kraftstoffproben (#1 bis #5) waren zudem mit handelsüblichem Mitteldestillat-kaltfließverbesserer (MDFI) und Wachs-Anti-Settling-Additiv (WASA) additiviert.All fuel samples (# 1 to # 5) were also additized with commercial middle distillate cold flow improver (MDFI) and wax anti-settling additive (WASA).
Den in folgender Tabelle zusammengefassten Testdaten ist zu entnehmen, dass die Delta CP und CFPPKS Werte der erfindungsgemäß additivierten DKs deutlich verbessert gegenüber den Imid-haltigen DKs sind. Mit der Amid-Additivierung kann somit das Kälteverhalten der DKs deutlich verbessert werden.
- CFPP: CFPP des Gesamtkraftstoffs
- CFPPKS: CFPP der Unterphase
- CPKS: CP der Unterphase
- DeltaCP: Differenz zum CP des nur mit Kaltfliessverbesserer additivierten Kraftstoffes, ohne Zugabe von Herstellungsbeispiel 1
oder 2
- CFPP: CFPP of total fuel
- CFPPKS: CFPP of the lower phase
- CPKS: CP of the lower phase
- DeltaCP: Difference to the CP of the fuel only additized with cold flow improver, without addition of Preparation Example 1 or 2
Die Bestimmung erfolgte nach den Vorgaben von DGMK-Report 531. Verwendetes Motorenöl: Wintershall 14W40 Multi Record Top Verwendeter Dieselkraftstoff (DK): RF-06-03 (Referenzdiesel, Haltermann Products, Hamburg)The determination was carried out according to the specifications of DGMK Report 531. Engine oil used: Wintershall 14W40 Multi Record Top Diesel fuel used (DK): RF-06-03 (reference diesel, Haltermann Products, Hamburg)
Das zu prüfende Additiv wird mit der gleichen Menge Mineralöl (je 10g) vermischt, 3 Tage bei 90°C konditioniert und dabei visuell bewertet. Anschließend wird das Gemisch mit Dieselkraftstoff auf 500 ml aufgefüllt, vermischt und mit Hilfe des SEDAB-Filtrationstests (ebenfalls definiert in DGMK-Report 531) beurteilt.The additive to be tested is mixed with the same amount of mineral oil (10 g each), conditioned for 3 days at 90 ° C. and assessed visually. The mixture is then made up to 500 ml with diesel fuel, mixed and evaluated by means of the SEDAB filtration test (likewise defined in DGMK Report 531).
Die Ergebnisse sind in folgender Tabelle zusammengefasst:
a)da beide Produkte synthesebedingt unterschiedliche Lösungsmitteltypen (Solvesso 150 bzw. Pilot 900) enthielten wurden diese vor Durchführung des Tests mit der gleichen Menge des jeweils anderen Lösungsmittels versetzt, so dass identischen Testbedingungen gegeben waren. a) since both products contained different types of solvents (Solvesso 150 or Pilot 900) due to the synthesis, they were mixed with the same amount of the other solvent before the test was carried out so that identical test conditions were met.
Die Bestimmung erfolgte in einem Personenkraftwagen-Betriebstest. Es wurde handelsüblicher Dieselkraftstoff (DK) EN590 (mit üblichen DK-Additiven additiviert) Das zu prüfende Additiv (erfindungsgemäßes Additiv gemäß Herstellungsbeispiel 1) wurde dem EN590 DK zugesetzt. Zum Vergleich dient handelsüblicher EN590 Kraftstoff, der nicht mit einem erfindungsgemäßen Additiv versetzt war. Nach Beeindingung des Motorentests werden die Injektoren auf Ablagerungen überprüft. Man beobachtet einen überraschend deutlichen positiven Effekt auf IDIDs.The determination was made in a passenger car operating test. Commercially available diesel fuel (DK) EN590 (additized with customary DK additives) The additive to be tested (inventive additive according to Preparation Example 1) was added to the EN590 DK. For comparison, commercial EN590 fuel is used, which was not mixed with an additive according to the invention. After completion of the engine test, the injectors are checked for deposits. A surprisingly significant positive effect on IDIDs is observed.
Ein Personenkraftwagen mit Common Rail-Injektoren (Magnettyp) bei denen Injektorablagerungen festgestellt worden waren, wurde zur Evaluierung des Additivs zur Entfernung dieser inneren Injektorablagerungen verwendet.A passenger car with common rail injectors (solenoid type) having injector deposits detected was used to evaluate the additive to remove these internal injector deposits.
Das Auftreten bräunlicher innerer Ablagerungen in den Injektoren wurde durch optische (visuelle) Inspektion der Armatur der Ansteuereinheit, der Ventilplatte vor der Armatur und der Ventilsitzfläche nachgewiesen und war außerdem über einen rauhen und geräuschvollen Motorlauf erkennbar. Den aus der ausgelesenen Daten konnte ebenfalls entnommen werden, dass die Menge des in den Zylinder injizierten Kraftstoffvolumens vom Normalwert deutlich abwich.The occurrence of brownish internal deposits in the injectors was evidenced by visual inspection of the drive unit armature, the valve plate in front of the armature and the valve seat surface, and was also detectable through rough and noisy engine running. It could also be seen from the data read that the quantity of fuel injected into the cylinder deviated significantly from the normal value.
Der Motor wurde zunächst auf der Straße mit einer Tankfüllung von herkömmlich additiviertem Diesel ohne erfindungsgemäßes Additiv EN590 Grundkraftstoff (50 Liter, 750 km im Mischbetrieb auf Autobahnen, Landstraßen und Innenstadt) betrieben. Es war keine Verbesserung bei den inneren Ablagerungen zu beobachten, wenn das Fahrzeug mit einer Tankfüllung nicht-additivierten Kraftstoffes betrieben wurde (vgl. folgende Tabelle).The engine was initially operated on the road with a tank of conventional additiertem diesel without inventive additive EN590 base fuel (50 liters, 750 km in mixed operation on highways, highways and downtown). There was no improvement in the internal deposits observed when the vehicle was operated on a tank of non-additive fuel (see the table below).
Im nächsten Schritt wurde der Tank mit dem gleichen EN590 Grundkraftstoff betrieben, der jedoch mit dem erfindungsgemäßen Additiv in einer Dosierung von 120 mg/kg aktives Material versetzt war. Der Wagen wurde erneut 750 km im Mischbetrieb gefahren. Die Ablagerungen waren nach diesem Testbetrieb mit additiviertem Kraftstoff nach 750 km deutlich verringert, wie bereits durch einen weicheren, weniger lauten Motorbetrieb feststellbar war. Auch die aus der Motorkontrolleinheit ausgelesenen Daten zeigten, dass die Mengen an eingespritztem Kraftstoff auf den Sollwert zurückgingen.In the next step, the tank was operated with the same EN590 base fuel, but with the additive according to the invention was added in a dosage of 120 mg / kg of active material. The car was again driven 750 km in mixed operation. The deposits were significantly reduced after this test operation with additized fuel after 750 km, as already by a softer, less noisy engine operation was detectable. Also, the data read from the engine control unit showed that the amounts of injected fuel decreased to the set point.
Nach zwei Tankfüllungen und Betrieb über 1500 km mit erfindungsgemäß additiviertem Kraftstoff waren die bräunlichen Injektorablagerungen aus der Armatur der Ansteuereinheit (solenoid coil face), der Ventilplatte vor der Armatur und der Ventilsitzfläche völlig verschwunden, wie nach dem Öffnen des Injektors visuell feststellbar war.After two tank fillings and operation over 1500 km with inventively additive fuel, the brownish Injektorablagerungen from the valve solenoid coil face, the valve plate in front of the fitting and the valve seat surface were completely gone, as was visually detectable after opening the injector.
Diese Ergebnisse veranschaulichen eindeutig, dass das erfindungsgemäße Additiv innere Injektorablagerungen (IDIDs) bei niedriger Dosierung völlig entfernen konnte. Aus den Versuchsergebnissen kann ebenfalls gefolgert werden, dass das Additiv außerdem die Fähigkeit besitzt, die Bildung von IDIDs auch bei geringeren Dosierungsraten zu verhindern. Darüber hinaus wurde festgestellt, dass das erfindungemäße Additiv nicht nur wachs- oder seifenartige IDIDs sondern auch feste, kohlenstoffartige, polymere Ablagerungen zu beseitigen in der Lage ist.
Auf die Offenbarung der hierin zitierten Druckschriften wird ausdrücklich Bezug genommen.Reference is expressly made to the disclosure of the references cited herein.
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PL2808350T3 (en) | 2018-04-30 |
AU2016200898A1 (en) | 2016-03-03 |
BR112013000297B1 (en) | 2020-10-06 |
EP2808350B1 (en) | 2017-10-25 |
AU2017228610A1 (en) | 2017-10-05 |
CN103080145B (en) | 2014-12-10 |
MX2013000054A (en) | 2013-03-18 |
CN103080145A (en) | 2013-05-01 |
PL3327044T3 (en) | 2021-07-19 |
EP3747915A1 (en) | 2020-12-09 |
EP3327044B1 (en) | 2020-10-28 |
HUE052753T2 (en) | 2021-05-28 |
PL2591016T3 (en) | 2015-07-31 |
BR112013000297A2 (en) | 2016-05-24 |
ES2844403T3 (en) | 2021-07-22 |
CA2804322A1 (en) | 2012-01-12 |
EP2808350A1 (en) | 2014-12-03 |
ES2655470T3 (en) | 2018-02-20 |
AU2019210580A1 (en) | 2019-08-22 |
JP2013532163A (en) | 2013-08-15 |
AU2016200898B2 (en) | 2017-06-15 |
ES2535192T3 (en) | 2015-05-06 |
EP2591016A1 (en) | 2013-05-15 |
WO2012004300A1 (en) | 2012-01-12 |
AU2011275778B2 (en) | 2016-03-03 |
KR101886453B1 (en) | 2018-08-07 |
EP2591016B1 (en) | 2015-01-21 |
AU2017228610B2 (en) | 2019-05-16 |
CA2804322C (en) | 2020-02-11 |
AU2011275778A1 (en) | 2013-01-24 |
KR20130041926A (en) | 2013-04-25 |
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